HERBICIDALLY ACTIVE CYCLIC DIONE COMPOUNDS, OR DERIVATIVES THEREOF, SUBSTITUTED BY A PHENYL WHICH HAS AN ALKYNYL-CONTAINING SUBSTITUENT

COMPOSES DIONES CYCLIQUES ACTIFS DU POINT DE VUE HERBICIDE, OU LEURS DERIVES, SUBSTITUES PAR UN GROUPE PHENYLE QUI PORTE UN SUBSTITUANT CONTENANT UN GROUPE ALCYNYLE

English Abstract

The present invention relates to a compound of formula (I), wherein: X is methyl or chlorine; R1 is methyl or chlorine; R2 is hydrogen, methyl, ethyl, n-propyl, cyclopropyl, vinyl, ethynyl, fluorine, chlorine, bromine, C1-C3alkoxy, C1-C2fluoroalkoxy, C1-C2alkoxy-C1-C3alkoxy- or C1fluoroalkoxy-C1-C3alkoxy-; and Y is O, S, S(O), S(O)2, N(C1-C2alkyl), N(C1-C2alkoxy), C(O), CR8R9 or -CR10R11CR12R13-; and and G, R3, R4, R5 and R6 are as defined herein; wherein the compound of formula (I) is optionally present as an agrochemically acceptable salt thereof. These compounds are suitable for use as herbicides. The invention therefore also relates to a method of controlling weeds, especially grassy monocotyledonous weeds, in crops of useful plants, comprising applying a compound of formula (I), or a herbicidal composition comprising such a compound, to the plants or to the locus thereof.

French Abstract

La présente invention porte sur un composé de formule (I), dans laquelle : X représente le groupe méthyle ou l'atome de chlore ; R1 représente le groupe méthyle ou l'atome de chlore ; R2 représente l'atome d'hydrogène, de fluor, de chlore ou de brome ou un groupe méthyle, éthyle, n-propyle, cyclopropyle, vinyle, éthynyle, alcoxy en C1-C3, fluoroalcoxy en C1-C2, (alcoxy en C1-C2)(alcoxy en C1-C3)- ou (fluoroalcoxy en C1)(alcoxy en C1-C3)- ; Y représente O, S, S(O), S(O)2, N(alkyle en C1-C2), N(alcoxy en C1-C2), C(O), CR8R9 ou -CR10R11CR12R13- ; et G, R3, R4, R5 et R6 sont tels que définis dans la description ; le composé de formule (I) étant éventuellement présent sous forme d'un sel acceptable en agrochimie de celui-ci. Ces composés sont appropriés pour être utilisés comme herbicides. L'invention porte également par conséquent sur un procédé de lutte contre des mauvaises herbes, en particulier des mauvaises herbes monocotylédones graminées, dans des cultures de plantes utiles, comprenant l'application d'un composé de formule (I), ou d'une composition herbicide comprenant un tel composé, sur les plantes ou sur leur locus.

Claims

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WE CLAIM:
1. A compound of formula (l):
<IMG>
wherein:
X is methyl or chlorine;
R1 is methyl or chlorine;
R2 is hydrogen, methyl, ethyl, n-propyl, cyclopropyl, vinyl, ethynyl,
fluorine, chlorine, bromine,
C1-C3alkoxy, C1-C2fluoroalkoxy, C1-C2alkoxy-C1-C3alkoxy-, or C1fluoroalkoxy-C1-
C3alkoxy-; and
R3, R4, R5 and R6, independently of each other, are hydrogen, C1-C5alkyl, C2-
C4alkenyl,
C2-C4alkynyl, C1-C2fluoroalkyl, C1-C3alkoxyC1-C3alkyl, C1-C3alkylthioC1-
C3alkyl,
C1-C3alkylsulfinylC1-C3alkyl, C1-C3alkylsulfonylC1-C3alkyl; C3-C4cycloalkyl;
or an unsubstituted 4,
or 6 membered monocyclic heterocyclyl having one ring heteroatom independently
selected
from oxygen, sulfur and nitrogen, and attached at a ring carbon atom within
the heterocyclyl;
provided that no more than one of R3, R4, R5 and R6 is alkenyl, alkynyl,
alkoxyalkyl,
alkylthioalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl, cycloalkyl or
heterocyclyl;
or R3 and R4 taken together are -(CH2)n1- or -(CH2)n2-X1-(CH2)n3- and R5 and
R6 are as defined
herein, or R5 and R6 taken together are -(CH2)n1- or -(CH2)n2-X1-(CH2)n3- and
R3 and R4 are as
defined herein;
wherein X1 is O, S, S(O), S(O)2, NH, N(C1-C2alkyl), N(C1-C2alkoxy), C(H)(C1-
C2alkyl),
C(C1-C2alkyl)2 or C(H)(C1-C2alkoxy);
n1 is 2, 3, 4 or 5; and
n2 and n3 are independently 1, 2 or 3 provided that n2 + n3 is 2, 3 or 4;

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or R4 and R5 taken together are -(CH2)n4- or -(CH2)n5-C(R7a)(R7b)-(CH2)n6- or -
C(R7c)=C(R7d)-;
wherein R7a is C1-C2alkyl or C1-C2alkoxy; and R7b is hydrogen or C1-C2alkyl
provided that R7b is
hydrogen when R7a is C1-C2alkoxy;
n4 is 1, 2 or 3; and
n5 and n6 are independently 0, 1 or 2 provided that n5 + n6 is 0, 1 or 2;
and R7C and R7d independently are hydrogen or C1-C2alkyl; and
Y is O, S, S(O), S(O)2, N(C1-C2alkyl), N(C1-C2alkoxy), C(O), CR8R9 or -
CR10R11CR12R13-; and
R5 and R9 are, independently of each other:
hydrogen, C1-C6alkyl, C2-C4alkenyl, C2-C4alkynyl, C1-C2fluoroalkyl, C1-
C3alkoxy1-C3alkyl,
C1-C3alkylthioC1-C3alkyl, C1-C3alkylsulfinylC1-C3alkyl, or C1-
C3alkylsulfonylC1-C3alkyl;
C3-C6cycloalkyl or C3-C6cycloalkyl substituted by one or two substituents
which
independently are C1-C3alkyl or C1-C2fluoroalkyl; and in which one ring CH2
moiety of a
C4-C6cycloalkyl is optionally replaced by an oxygen or sulfur atom or by a
S(O), S(O)2, NH,
N(C1-C3alkyl), N(C1-C2fluoroalkyl), N[C(O)C1-C3alkyl], N[C(O)1-C2fluoroalkyl]
or N(C1-C2alkoxy)
moiety;
C3-C6cycloalkyl substituted by one substituent being C1-C3alkoxy and
optionally further
substituted by one substituent being C1-C2alkyl;
C5-C6cycloalkenyl or C5-C6cycloalkenyl substituted by one or two C1-C3alkyl
substituents;
C3-C6cycloalkylC1-C2alkyl- or C3-C6cycloalkylC1-C2alkyl- substituted by one or
two ring
substituents which independently are C1-C3alkyl or C1-C2fluoroalkyl; and in
which one ring CH2
moiety of a C4-C6cycloalkylC1-C2alkyl- is optionally replaced by an oxygen or
sulfur atom or by a
S(O), S(O)2, NH, N(C1-C2alkyl), N(C1-C2fluoroalkyl), N[C(O)C1-C3alkyl],
N[C(O)C1-C2fluoroalkyl]
or N(C1-C2alkoxy) moiety;
C3-C6cycloalkylC1-C2alkyl- substituted by one ring substituent being C1-
C3alkoxy and
optionally further substituted by one ring substituent being C1-C2alkyl; or
Het or Het-CH2-, wherein Het is a heteroaryl, attached at a ring-carbon, which
is optionally
substituted by 1, 2 or 3 ring-carbon substituents independently being C1-
C3alkyl,
C1-C2fluoroalkyl, C1-C3alkyl-C(O)-, C1-C2fluoroalkyl-C(O)-, hydroxy, C2-
C3alkenyl, C2-C3alkynyl,
C1-C3alkoxy, C1-C2fluoroalkoxy, halogen, cyano or nitro, provided that any non-
fluorine halogen,
alkoxy or fluoroalkoxy is not substituted at any ring-carbon bonded directly
to a ring-nitrogen of

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the heteroaryl; and/or, in the case of a 5-membered heteroaryl ring containing
a ring-nitrogen
atom not partaking in a C=N ring double bond, the heteroaryl is optionally
substituted on the
ring-nitrogen atom not partaking in a C=N ring double bond by one C1-C3alkyl,
C1-C2fluoroalkyl,
C1-C3alkyl-C(O)-, C1-C2fluoroalkyl-C(O)- or C1-C2alkyl-S(O)2- substituent;
provided that no more than one of R8 and R9 is an optionally substituted
cycloalkyl; an optionally
substituted cycloalkyl in which one ring CH2 moiety has been replaced by an
oxygen or sulfur
atom or by a S(O), S(O)2, NH, N(C1-C3alkyl), N(C1-C2fluoroalkyl), N[C(O)C1-
C3alkyl],
N[C(O)C1-C2fluoroalkyl] or N(C1-C2alkoxy) moiety; an optionally substituted
cycloalkenyl; an
optionally substituted cycloalkyl-alkyl-; an optionally substituted cycloalkyl-
alkyl- in which one
ring CH2 moiety has been replaced by an oxygen or sulfur atom or by a S(O),
S(O)2, NH, N(C1-
C3alkyl), N(C1-C2fluoroalkyl), N[C(O)C1-C3alkyl], N[C(O)C1-C2fluoroalkyl] or
N(C1-C2alkoxy)
moiety; or Het or Het-CH2-;
or R9 is hydrogen or C1-C2alkyl, and R9 is C1-C2alkoxy;
or R8 and R9 taken together are -(CH2)n7- or -(CH2)n8-X2-(CH2)n9-;
wherein X2 is O, S, S(O), S(O)2, NH, N(C1-C3alkyl), N(C1-C2fluoroalkyl),
N[C(O)C1-C3alkyl],
N[C(O)C1-C2fluoroalkyl], N(C1-C2alkoxy), C(H)(C1-C3alkyl), C(C1-C2alkyl)2 or
C(H)(C1-C3alkoxy);
n7 is 2, 3, 4, 5 or 6; and
n8 and n9 are independently 0, 1, 2 or 3 provided that n8 + n9 is 2, 3, 4 or
5; and
R10, R11, R12 and R13 are independently of each other hydrogen or C1-C4alkyl
provided that no
more than one of R19, R11, R12 and R13 is C3-C4alkyl; and
and wherein:
G is hydrogen; an agriculturally acceptable metal, or an agriculturally
acceptable sulfonium or
ammonium group; or
G is -C(X a)-R a, -C(X b)-X c-R b, -C(X d)-N(R c)-R d, -SO2-R e, -ID(X e)(R f)-
R g, -CH2-X f-R h; or
phenyl-CH2- or phenyl-CH(C1-C2alkyl)- (in each of which the phenyl is
optionally substituted by
1, 2 or 3 of, independently, C1-C2alkyl, C1fluoroalkyl, C1-C2alkoxy,
C1fluoroalkoxy, fluorine,

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chlorine, bromine, cyano or nitro), or heteroaryl-CH2- or heteroaryl-CH(C1-
C2alkyl)- in each of
which the heteroaryl is optionally substituted by 1, 2 or 3 of, independently,
C1-C2alkyl,
C1fluoroalkyl, C1-C2alkoxy, C1fluoroalkoxy, fluorine, chlorine, bromine, cyano
or nitro, or
phenyl-C(O)-CH2- wherein the phenyl is optionally substituted by 1, 2 or 3 of,
independently, C1-
C2alkyl, C1fluoroalkyl, C1-C2alkoxy, C1fluoroalkoxy, fluorine, chlorine,
bromine, cyano or nitro; or
C1-C8alkoxy-C(O)-CH2-, C1-C8alkoxy-C(O)-CH=CH-, C2-C7alken-1-yl-CH2-, C2-
C7alken-1-
yl-CH(C1-C2alkyl)-, C2-C4fluoroalken-1-yl-CH2-, C2-C7alkyn-1-yl-CH2-, or C2-
C7alkyn-1-yl-CH(C1-C2alkyl)-;
wherein X a, X b, X c, X d, X e and X f are independently of each other oxygen
or sulfur; and wherein
R a is H, C1-C21alkyl, C2-
C21alkenyl, C2-C18alkynyl, C1-10fluoroalkyl, C1-C10cyanoalkyl, C1-
C10nitroalkyl,C1-C10aminoalkyl, C1-C5alkylamino(C1-C5)alkyl, C2-
C8dialkylamino(C1-C5)alkyl, C3-
C7cycloalkyl(C1-C5)alkyl, C1-C5alkoxy(C1-C5)alkyl, C3-C5alkenyloxy(C1-
C5)alkyl, C3-C5alkynyloxy
(C1-C5)alkyl, C1-C5alkylthio(C1-C5)alkyl, C1-C5alkylsulfinyl(C1-C5)alkyl, C1-
C5alkylsulfonyl(C1-
C5)alkyl, C2-C8alkylideneaminoxy(C1-C5)alkyl, C1-C5alkylcarbonyl(C1-C5)alkyl,
C1-
C5alkoxycarbonyl(C1-C5)alkyl, aminocarbonyl(C1-C5)alkyl, C1-
C5alkylaminocarbonyl(C1-C5)alkyl,
C2-C8dialkylaminocarbonyl(C1-C5)alkyl, C1-C5alkylcarbonylamino(C1-C5)alkyl, N-
(C1-
C5)alkylcarbonyl-N-(C1-C5)alkylamino(C1-C5)alkyl, C3-C8trialkylsilyl(C1-
C5)alkyl, phenyl(C1-
C5)alkyl (wherein the phenyl is optionally substituted by 1, 2 or 3 of,
independently, C1-C3alkyl,
C1-C3fluoroalkyl, C1-C3alkoxy, C1-C3fluoroalkoxy, C1-C3alkylthio, C1-
C3alkylsulfinyl, C1-
C3alkylsulfonyl, halogen, cyano, or nitro), heteroaryl(C1-C5)alkyl (wherein
the heteroaryl is
optionally substituted by 1, 2 or 3 of, independently, C1-C3alkyl, C1-
C3fluoroalkyl, C1-C3alkoxy,
C1-C3fluoroalkoxy, C1-C3alkylthio,C1-C3alkysulfinyl, C1-C3alkylsulfonyl,
halogen, cyano, or
nitro), C2-C5fluoroalkenyl, C3-C8cycloalkyl; phenyl or phenyl substituted by
1, 2 or 3 of,
independently, C1-C3alkyl, C1-C3fluoroalkyl, C1-C3alkoxy, C1-C3fluoroalkoxy,
halogen, cyano or
nitro; or heteroaryl or heteroaryl substituted by 1, 2 or 3 of, independently,
C1-C3 alkyl, C1-
C3fluoroalkyl, C1-C3alkoxy, C1-C3fluoroalkoxy, halogen, cyano or nitro;
R b is C1-C18alkyl, C3-C18alkenyl, C3-C18alkynyl, C2-C10fluoroalkyl, C1-
C10cyanoalkyl, C1-
C10nitroalkyl, C2-C10aminoalkyl, C1-C5alkylamino(C1-C5)alkyl, C2-
C8dialkylamino(C1-C5)alkyl, C3-
C7cycloalkyl(C1-C5)alkyl, C1-C5alkoxy(C1-C5)alkyl, C3-C5alkenyloxy(C1-
C5)alkyl, C3-
C5alkynyloxy(C1-C5)alkyl, C1-C5alkylthio(C1-C5)alkyl, C1-C5alkylsulfinyl(C1-
C5)alkyl, C1-

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C5alkylsulfonyl(C1-C5)alkyl, C2-C8alkylideneaminoxy(C1-C5)alkyl, C1-
C5alkylcarbonyl(C1-C5)alkyl,
C1-C5alkoxycarbonyl(C1-C5)alkyl, aminocarbonyl(C1-C5)alkyl, C1-
C5alkylaminocarbonyl(C1-
C5)alkyl, C2-C8dialkylaminocarbonyl(C1-C5)alkyl, C1-C5alkylcarbonylamino(C1-
C5)alkyl, N-(C1-
C5)alkylcarbonyl-N-(C1-C5)alkylamino(C1-C5)alkyl, C3-C6trialkylsilyl(C1-
C5)alkyl, phenyl(C1-
C5)alkyl wherein the phenyl is optionally substituted by 1, 2 or 3 of,
independently, C1-C3alkyl,
C1-C3fluoroalkyl, C1-C3alkoxy, C1-C3fluoroalkoxy, C1-C3alkylthio, C1-
C3alkylsulfinyl, C1-
C3alkylsulfonyl, halogen, cyano, or nitro, heteroarylC1-C5alkyl wherein the
heteroaryl is
optionally substituted by 1, 2 or 3 of, independently, C1-C3alkyl, C1-
C3fluoroalkyl, C1-C3alkoxy,
C1-C3fluoroalkoxy, C1-C3alkyl-thio, C1-C3alkylsulfinyl, C1-C3alkylsulfonyl,
halogen, cyano, or
nitro, C3-C5fluoroalkenyl, C3-C8cycloalkyl; phenyl or phenyl substituted by 1,
2 or 3 of,
independently, C1-C3alkyl, C1-C3fluoroalkyl, C1-C3alkoxy, C1-C3fluoroalkoxy,
halogen, cyano or
nitro; or heteroaryl or heteroaryl substituted by 1, 2 or 3 of, independently,
C1-C3 alkyl, C1-
C3fluoroalkyl, C1-C3alkoxy, C1-C3fluoroalkoxy, halogen, cyano or nitro; and
Rc and Rd are each independently of each other hydrogen, C1-C10alkyl, C3-
C10alkenyl, C3-
C10alkynyl, C2-C10fluoroalkyl, C1-C10cyanoalkyl, C1-C10nitroalkyl, C1-
C10aminoalkyl, C1-
C5alkylamino(C1-C5)alkyl, C2-C8dialkylamino(C1-C5)alkyl, C3-C7cycloalkyl(C1-
C5)alkyl, C1-
C5alkoxy(C1-C5)alkyl, C3-C5alkenyloxy(C1-C5)alkyl, C3-C5alkynyloxy(C1-
C5)alkyl, C1-
C5alkylthio(C1-C5)alkyl, C1-C5alkylsulfinyl(C1-C5)alkyl, C1-C5alkylsulfonyl(C1-
C5)alkyl, C2-
C8alkylideneaminoxy(C1-C5)alkyl, C1-C5alkylcarbonyl(C1-C5)alkyl, C1-
C5alkoxycarbonyl(C1-
C5)alkyl, aminocarbonyl(C1-C5)alkyl, C1-C5alkylaminocarbonyl(C1-C5)alkyl, C2-
C8dialkylaminocarbonyl(C1-C5)alkyl, C1-C5alkylcarbonylamino(C1-C5)alkyl, N-(C1-
C5)alkylcarbonyl-N-(C2-C5)alkylaminoalkyl, C3-C6trialkylsilyl(C1-C5)alkyl,
phenyl(C1-C5)alkyl
(wherein the phenyl is optionally substituted by 1, 2 or 3 of, independently,
C1-C3alkyl, C1-
C3fluoroalkyl, C1-C3alkoxy, C1-C3fluoroalkoxy, C1-C3alkylthio, C1-
C3alkylsulfinyl, C1-
C3alkylsulfonyl, halogen, cyano, or nitro), heteroaryl(C1-C5)alkyl (wherein
the heteroaryl is
optionally substituted by 1, 2 or 3 of, independently, C1-C3alkyl, C1-
C3fluoroalkyl, C1-C3alkoxy,
C1-C3fluoroalkoxy, C1-C3alkylthio, C1-C3alkylsulfinyl, C1-C3alkylsulfonyl,
halogen, cyano, or
nitro), C2-C5fluoroalkenyl, C3-C8cycloalkyl; phenyl or phenyl substituted by
1, 2 or 3 of,
independently, C1-C3alkyl, C1-C3fluoroalkyl, C1-C3alkoxy, C1-C3fluoroalkoxy,
halogen, cyano or
nitro; heteroaryl or heteroaryl substituted by 1, 2 or 3 of, independently, C1-
C3alkyl, C1-
C3fluoroalkyl, C1-C3alkoxy, C1-C3fluoroalkoxy, halogen, cyano or nitro;
heteroarylamino or
heteroarylamino substituted by 1, 2 or 3 of, independently, C1-C3alkyl, C1-
C3fluoroalkyl, C1-

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C3alkoxy, C1-C3fluoroalkoxy, halogen, cyano or nitro; diheteroarylamino or
diheteroarylamino
substituted by 1, 2 or 3 of, independently, C1-C3alkyl, C1-C3fluoroalkyl, C1-
C3alkoxy, C1-
C3fluoroalkoxy, halogen, cyano or nitro; phenylamino or phenylamino
substituted by 1, 2 or 3 of,
independently, C1-C3alkyl, C1-C3fluoroalkyl, C1-C3alkoxy, C1-C3fluoroalkoxy,
halogen, cyano or
by nitro; diphenylamino or diphenylamino substituted by 1, 2 or 3 of,
independently, C1-C3alkyl,
C1-C3fluoroalkyl, C1-C3alkoxy, C1-C3fluoroalkoxy, halogen, cyano or nitro; or
C3-
C7cycloalkylamino, di(C3-C7cycloalkyl)amino or C3-C7cycloalkoxy;
or Rc and Rd, together with the nitrogen to which they are bonded, to form an
unsubstituted 4, 5,
6 or 7 membered ring, optionally containing one heteroatom selected from O or
S; and
Re is C1-C10alkyl, C2-C10alkenyl, C2-C10alkynyl, C1-C10fluoroalkyl, C1-
C10cyanoalkyl, C1-
C10nitroalkyl, C1-C10aminoalkyl, C1-C5alkylamino(C1-C5)alkyl, C2-
C8dialkylamino(C1-C5)alkyl, C3-
C7cycloalkyl(C1-C5)alkyl, C1-C5alkoxy(C1-C5)alkyl, C3-C5alkenyloxy(C1-
C5)alkyl, C3-
C5alkynyloxy(C1-C5)alkyl, C1-C5alkylthio(C1-C5)alkyl, C1-C5alkylsulfinyl(C1-
C5)alkyl, C1-
C5alkylsulfonyl(C1-C8)alkyl, C2-C8alkylideneaminoxy(C1-C8)alkyl, C1-
C5alkylcarbonyl(C1-C8)alkyl,
C1-C5alkoxycarbonyl(C1-C5)alkyl, aminocarbonyl(C1-C5)alkyl, C1-
C5alkylaminocarbonyl(C1-
C5)alkyl, C2-C8dialkylaminocarbonyl(C1-C5)alkyl, C1-C5alkylcarbonylamino(C1-
C5)alkyl, N-(C1-
C5)alkylcarbonyl-N-(C1-C5)alkylamino(C1-C5)alkyl, C3-C8trialkylsilyl(C1-
C5)alkyl, phenyl(C1-
C8)alkyl (wherein the phenyl is optionally substituted by 1, 2 or 3 of,
independently, C1-C3alkyl,
C1-C3fluoroalkyl, C1-C3alkoxy, C1-C3fluoroalkoxy, C1-C3alkylthio, C1-
C3alkylsulfinyl, C1-
C3alkylsulfonyl, halogen, cyano, or nitro), heteroaryl(C1-C5)alkyl (wherein
the heteroaryl is
optionally substituted by 1, 2 or 3 of, independently, C1-C3alkyl, C1-
C3fluoroalkyl, C1-C3alkoxy,
C1-C3fluoroalkoxy, C1-C3alkylthio, C1-C3alkylsulfinyl, C1-C3alkylsulfonyl,
halogen, cyano, or
nitro), C2-C5fluoroalkenyl, C3-C8cycloalkyl; phenyl or phenyl substituted by
1, 2 or 3 of,
independently, C1-C3alkyl, C1-C3fluoroalkyl, C1-C3alkoxy, C1-C3fluoroalkoxy,
halogen, cyano or
nitro; heteroaryl or heteroaryl substituted by 1, 2 or 3 of, independently, C1-
C3alkyl, C1-
C3fluoroalkyl, C1-C3alkoxy, C1-C3fluoroalkoxy, halogen, cyano or nitro;
heteroarylamino or
heteroarylamino substituted by 1, 2 or 3 of, independently, C1-C3 alkyl, C1-
C3fluoroalkyl, C1-
C3alkoxy, C1-C3fluoroalkoxy, halogen, cyano or nitro; diheteroarylamino or
diheteroarylamino
substituted by 1, 2 or 3 of, independently, C1-C3alkyl, C1-C3fluoroalkyl, C1-
C3alkoxy, C1-
C3fluoroalkoxy, halogen, cyano or nitro; phenylamino or phenylamino
substituted by 1, 2 or 3 of,
independently, C1-C3alkyl, C1-C3fluoroalkyl, C1-C3alkoxy, C1-C3fluoroalkoxy,
halogen, cyano or
nitro; diphenylamino or diphenylamino substituted by 1, 2 or 3 of,
independently, C1-C3alkyl, C1-

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C3fluoroalkyl, C1-C3alkoxy, C1-C3fluoroalkoxy, halogen, cyano or nitro; or C3-
C7cycloalkylamino,
di(C3-C7cycloalkyl)amino, C3-C7cycloalkoxy, C1-C10alkoxy, C1-C10fluoroalkoxy,
C1-C5alkylamino
or di(C1-C4alkyl)amino;
Rf and Rg are are each independently of each other C1-C10alkyl, C2-C10alkenyl,
C2-C10alkynyl,
C1-C10alkoxy, C1-C10fluoroalkyl, C1-C10cyanoalkyl, C1-C10nitroalkyl, C1-
C10aminoalkyl, C1-
C5alkylamino(C1-C5)alkyl, C2-C8dialkylamino(C1-C5)alkyl, C3-C7cycloalkyl(C1-
C5)alkyl, C1-
C5alkoxy(C1-C5)alkyl, C3-C5alkenyloxy(C1-C5)alkyl, C3-C5alkynyloxy(C1-
C5)alkyl, C1-C5alkylthio(C1-
C5)alkyl, C1-C5alkylsulfinyl(C1-C5)alkyl, C1-C5alkylsulfonyl(C1-C5)alkyl, C2-
C8alkylideneaminoxy(C1-C5)alkyl, C1-C5alkylcarbonyl(C1-C5)alkyl, C1-
C5alkoxycarbonyl(C1-
C5)alkyl, aminocarbonyl(C1-C5)alkyl, C1-C5alkylaminocarbonyl(C1-C5)alkyl, C2-
C8dialkylaminocarbonyl(C1-C5)alkyl, C1-C5alkylcarbonylamino(C1-C5)alkyl, N-(C1-
C5)alkylcarbonyl-N-(C2-C5)alkylaminoalkyl, C3-C8trialkylsilyl(C1-C5)alkyl,
phenyl(C1-C5)alkyl
(wherein the phenyl is optionally substituted by 1, 2 or 3 of, independently,
C1-C3alkyl, C1-
C3fluoroalkyl, C1-C3alkoxy, C1-C3fluoroalkoxy, C1-C3alkylthio, C1-
C3alkylsulfinyl, C1-
C3alkylsulfonyl, halogen, cyano, or nitro), heteroaryl(C1-C5)alkyl (wherein
the heteroaryl is
optionally substituted by 1, 2 or 3 of, independently, C1-C3alkyl, C1-
C3fluoroalkyl, C1-C3alkoxy,
C1-C3fluoroalkoxy, C1-C3alkylthio, C1-C3alkylsulfinyl, C1-C3alkylsulfonyl,
halogen, cyano, or
nitro), C2-C5fluoroalkenyl, C3-C8cycloalkyl; phenyl or phenyl substituted by
1, 2 or 3 of,
independently, C1-C3alkyl, C1-C3fluoroalkyl, C1-C3alkoxy, C1-C3fluoroalkoxy,
halogen, cyano or
nitro; heteroaryl or heteroaryl substituted by 1, 2 or 3 of, independently, C1-
C3 alkyl, C1-
C3fluoroalkyl, C1-C3alkoxy, C1-C3fluoroalkoxy, halogen, cyano or nitro;
heteroarylamino or
heteroarylamino substituted by 1, 2 or 3 of, independently, C1-C3 alkyl, C1-
C3fluoroalkyl, C1-
C3alkoxy, C1-C3fluoroalkoxy, halogen, cyano or nitro; diheteroarylamino or
diheteroarylamino
substituted by 1, 2 or 3 of, independently, C1-C3 alkyl, C1-C3fluoroalkyl, C1-
C3alkoxy, C1-
C3fluoroalkoxy, halogen, cyano or nitro; phenylamino or phenylamino
substituted by 1, 2 or 3 of,
independently, C1-C3alkyl, C1-C3fluoroalkyl, C1-C3alkoxy, C1-C3fluoroalkoxy,
halogen, cyano or
nitro; diphenylamino or diphenylamino substituted by 1, 2 or 3 of,
independently, C1-C3alkyl, C1-
C3fluoroalkyl, C1-C3alkoxy, C1-C3fluoroalkoxy, halogen, cyano or nitro; or C3-
C7cycloalkylamino,
di(C3-C7cycloalkyl)amino, C3-C7cycloalkoxy, C1-C10fluoroalkoxy, C1-
C5alkylamino or di(C1-
C4alkyl)amino; or benzyloxy or phenoxy, wherein the benzyl and phenyl groups
are in turn
optionally substituted by 1, 2 or 3 of, independently, C1-C3alkyl, C1-
C3fluoroalkyl, C1-C3alkoxy,
C1-C3fluoroalkoxy, halogen, cyano or nitro; and

- 229 -
Rh is C1-C10alkyl, C3-C10alkenyl, C3-C10alkynyl, C1-C10fluoroalkyl, C1-
C10cyanoalkyl, C1-
C10nitroalkyl, C2-C10aminoalkyl, C1-C5alkylamino(C1-C5)alkyl, C2-
C8dialkylamino(C1-C5)alkyl, C3-
C7cycloalkyl(C1-C5)alkyl, C1-C5alkoxy(C1-C5)alkyl, C3-C5alkenyloxy(C1-
C5)alkyl, C3-
C5alkynyloxy(C1-C5)alkyl, C1-C5alkylthio(C1-C5)alkyl, C1-C5alkylsulfinyl(C1-
C5)alkyl, C1-
C5alkylsulfonyl(C1-C5)alkyl, C2-C8alkylideneaminoxy(C1-C5)alkyl, C1-
C5alkylcarbonyl(C1-C5)alkyl,
C1-C5alkoxycarbonyl(C1-C5)alkyl, aminocarbonyl(C1-C5)alkyl, C1-
C5alkylaminocarbonyl(C1-
C5)alkyl, C2-C8dialkylaminocarbonyl(C1-C5)alkyl, C1-C5alkylcarbonylamino(C1-
C5)alkyl, N-(C1-
C5)alkylcarbonyl-N-(C1-C5)alkylamino(C1-C5)alkyl, C3-C8trialkylsilyl(C1-
C5)alkyl, phenyl(C1-
C5)alkyl (wherein the phenyl is optionally substituted by 1, 2 or 3 of,
independently, C1-C3alkyl,
C1-C3fluoroalkyl, C1-C3alkoxy, C1-C3fluoroalkoxy, C1-C3alkylthio, C1-
C3alkylsulfinyl, C1-C3
alkylsulfonyl, halogen, cyano or nitro), heteroaryl(C1-C5)alkyl (wherein the
heteroaryl is
optionally substituted by 1, 2 or 3 of, independently, C1-C3alkyl, C1-
C3fluoroalkyl, C1-C3alkoxy,
C1-C3fluoroalkoxy, C1-C3alkylthio, C1-C3alkylsulfinyl, C1-C3 alkylsulfonyl,
halogen, cyano or
nitro), phenoxy(C1-C5)alkyl (wherein the phenyl is optionally substituted by
1, 2 or 3 of,
independently, C1-C3alkyl, C1-C3fluoroalkyl, C1-C3alkoxy, C1-C3fluoroalkoxy,
C1-C3alkylthio, C1-
C3alkylsulfinyl, C1-C3 alkylsulfonyl, halogen, cyano or nitro),
heteroaryloxy(C1-C5)alkyl (wherein
the heteroaryl is optionally substituted by 1, 2 or 3 of, independently, C1-
C3alkyl, C1-
C3fluoroalkyl, C1-C3alkoxy, C1-C3fluoroalkoxy, C1-C3alkylthio, C1-
C3alkylsulfinyl, C1-C3
alkylsulfonyl, halogen, cyano or nitro), C3-C5fluoroalkenyl, C3-C8cycloalkyl;
phenyl or phenyl
substituted by 1, 2 or 3 of, independently, C1-C3alkyl, C1-C3fluoroalkyl, C1-
C3alkoxy, C1-
C3fluoroalkoxy, halogen, cyano or nitro; or heteroaryl or heteroaryl
substituted by 1, 2 or 3 of,
independently, C1-C3alkyl, C1-C3fluoroalkyl, C1-C3alkoxy, C1-C3fluoroalkoxy,
halogen, cyano or
nitro; C1-C6alkyl-C(O)-; or phenyl-C(O)- wherein the phenyl is optionally
substituted by 1 or 2 of,
independently, C1-C2alkyl, C1fluoroalkyl, C1-C2alkoxy, C1fluoroalkoxy,
fluorine, chlorine,
bromine, cyano or nitro;
wherein "heteroaryl" means an aromatic ring system containing at least one
ring heteroatom
and consisting either of a single ring or of two fused rings.
2. The compound as claimed in claim 1, wherein the compound of formula (I) is
present as an
agrochemically acceptable salt thereof.

- 230 -
3. The compound as claimed in claim 1 or 2, wherein G is hydrogen; an
agriculturally
acceptable metal, or an agriculturally acceptable sulfonium or ammonium group;
or G is -C(Xa)-
Ra or -C(Xb)-Xc-Rb, wherein Xa, Ra, Xb, XC and Rb are as defined herein.
4. The compound as claimed in any one of claims 1 to 3, wherein X is methyl.
5. The compound as claimed in any one of claims 1 to 4, wherein R1 is
chlorine.
6. The compound as claimed in any of claims 1 to 5, wherein R2 is methyl or
methoxy.
7. The compound as claimed in any one of claims 1 to 6, wherein: R1 is
chlorine, and R2 is
methoxy.
8. The compound as claimed in any one of claims 1 to 7, wherein R3, R4, R5 and
R6,
independently of each other, are hydrogen or C1-C2alkyl;
or R4 and R5 taken together are -(CH2)n4- wherein n4 is 2 or 3.
9. The compound as claimed in any one of claims 1 to 8, wherein Y is CR8R9.
10. The compound as claimed in claim 1 or 2, wherein the compound of formula
(l) is a
compound of one of the following types, described and illustrated below,
optionally present as
an agrochemically acceptable salt thereof:

- 231 -
<IMG>

- 232 -
<IMG>
wherein:
R1 is methyl, X is methyl, and R2 is hydrogen, methyl, chlorine, methoxy,
ethynyl, ethyl, vinyl, 2-
methoxyethoxy or ethoxy; or
R1 is chlorine, X is methyl, and R2 is hydrogen, chlorine, methoxy, ethynyl,
ethyl, vinyl,
2-methoxyethoxy or ethoxy; or
R1 is methyl, X is chlorine, and R2 is hydrogen, methyl, chlorine, methoxy,
ethynyl, ethyl, vinyl,
2-methoxyethoxy or ethoxy; or
R1 is chlorine, X is chlorine, and R2 is hydrogen, chlorine, methoxy, ethynyl,
ethyl, vinyl,
2-methoxyethoxy or ethoxy.
11. The compound as claimed in claim 1 or 2, which is compound A-1, A-2, A-3,
A-4, A-5, A-6,
A-7, A-8, A-9, A-10, A-11, A-12, A-13, A-14 or A-15, as illustrated below,
optionally present as
an agrochemically acceptable salt thereof:

- 233 -
<IMG>

- 234 -
<IMG>
12. The compound as claimed claim 1 or 2, which is compound A-20, A-22, A-25,
A-27, A-28,
A-30, A-31, A-32, A-33, A-34, A-35, A-36, A-37, A-38, A-39, A-40 or A-41, as
illustrated below,
optionally present as an agrochemically acceptable salt thereof:
<IMG>

- 235 -
<IMG>
13. A herbicidal composition which comprises the compound of formula (l), as
defined in any of
claims 1 to 12, and an agrochemically acceptable carrier, diluent and/or
solvent.

- 236 -
14. The herbicidal composition according to claim 13, which comprises one or
more further
herbicides and/or a safener.
15. A method of controlling weeds in crops of useful plants, comprising
applying the compound
of formula (l), as defined in any of claims 1 to 12, or a herbicidal
composition comprising such a
compound, to the plants or to the locus thereof.

Description

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Herbicidally active cyclic dione compounds, or derivatives thereof,
substituted by a
phenyl which has an alkynyl-containing substituent
The present invention relates to herbicidally active cyclic diones, in
particular pyrandione,
thiopyrandione, cyclohexanedione, alkanediyl-bridged cyclohexanedione,
cyclohexanetrione
or cycloheptanedione compounds, or derivatives thereof (e.g. enol ketone
tautomer
derivatives thereof), to processes for their preparation, to herbicidal
compositions comprising
those compounds, and to their use in controlling weeds such as grassy
monocotyledonous
weeds, especially in crops of useful plants, or in inhibiting undesired plant
growth. In
particular, the present invention relates to herbicidally active cyclic dione
compounds, or
derivatives thereof (e.g. enol ketone tautomer derivatives thereof), which are
substituted by a
phenyl which has an alkynyl-containing substituent.
WO 01/17972 A2 (Syngenta Participations AG) discloses phenyl-substituted (such
as
4-methyl-2,6-diethyl-phenyl- substituted) heterocycles suitable for use as
herbicides.
WO 03/013249 Al (Bayer AG) and its equivalent US 2005/0054535 Al disclose
selective
herbicidal compositions cornprising (a) a (substituted-phenyl)-substituted
cyclic ketoenol and
(b) a compound which improves crop plant compatibility, in particular
cloquintocet-mexyl or
mefenpyr-diethyl.
WO 2007/068427 A2 (Bayer CropScience AG) and its equivalent US 2009/0227563 Al
disclose a composition comprising (a) a (substituted-phenyl)-substituted
cyclic ketoenol as a
herbicide, and (b) an ammonium or phosphonium salt to boost activity.
WO 2008/071405 Al and WO 2009/074314 Al (both Syngenta Limited and Syngenta
Participations AG) each disclose herbicidally active pyran-3,5-diones,
thiopyran-3,5-diones
and cyclohexane-1,3,5-triones, each substituted at the 4-position of the
cyclic dione or trione
by an aryl-substituted-phenyl or by a heteroaryl-substituted-phenyl.
WO 2010/081755 Al and WO 2010/089211 Al (both Syngenta Limited) each disclose
herbicidally active pyran-3,5-diones, thiopyran-3,5-diones, cyclohexanediones,
cycloheptanediones and cyclohexanetriones, each substituted by an aryloxy-
substituted-
phenyl or by a heteroaryloxy-substituted-phenyl.

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WO 2008/110308 Al (Syngenta Participations AG) discloses 2-(substituted-
phenyl)-
cyclohexane-1,3-dione compounds and derivatives, containing a R8-X-(CR6R7)n-
substituent
(wherein X is 0, S, S(0) or S(0)2) or a heteroatom-containing-spirocyle at the
5-position of
the cyclohexane-1,3-dione, and having herbicidal properties. WO 2008/110307 Al
(Syngenta Participations AG) discloses 2-(substituted-phenyl)-5-heterocyclyl-
cyclohexane-
1,3-dione compounds and derivatives, and their use as herbicides. WO
2010/046194 Al
(Syngenta Limited) discloses 2-(substituted-phenyl)-cyclohexane-1,3-dione
compounds and
derivatives, containing a Q-CR6R7- substituent at the 5-position of the
cyclohexane-1,3-dione
(wherein Q is a saturated or mono-unsaturated heterocycle), and having
herbicidal
.. properties.
WO 2008/145336 Al and A8 (Syngenta Limited) disclose herbicidally active
phenyl-
substituted bicyclic (carbon-bridged, e.g. alkanediyl-bridged) 1,3-dione
compounds, such as
3-(substituted-phenyl)-bicyclo[3.2.1]octane-2,4-diones.
Copending PCT application PCT/EP2012/074118, filed on 30 November 2012 and
published
on 6 June 2013 as WO 2013/079672 Al (Syngenta Limited and Syngenta
Participations AG)
discloses that certain substituted spiroheterocyclic pyrrolidine dione
compounds, having an
alkynyl-phenyl- headgroup, have herbicidal properties.
Copending PCT application PCT/EP2012/074172, filed on 30 November 2012 and
published
on 6 June 2013 as WO 2013/079708 Al (Syngenta Limited and Syngenta
Participations AG)
discloses cyclopentane-1,3-dione compounds and derivatives (e.g. fused and/or
spirocyclic
bicyclic derivatives) thereof, which are substituted at the 2-position of the
cyclopentane-1,3-
dione by a phenyl which itself is substituted at the 4-position by
(specifically) either
prop-l-ynyl or chloroethynyl, and derivatives of the enol ketone tautomer of
such
cyclopentanediones, which have herbicidal activity and/or plant-growth-
inhibiting properties,
especially in the control of grassy monocotyledonous weeds and/or when used
post-
emergence.
Cyclic dione compounds have now been found, in particular pyran-3,5-dione,
thiopyran-3,5-
dione, cyclohexane-1,3-dione, alkanediyl-bridged cyclohexane-1,3-dione,
cyclohexane-1,3,5-
trione or cycloheptane-1,3-dione compounds, which are substituted, at the ring-
carbon atom
of the cyclic dione which is between the two oxo-substituted ring-carbons of
the cyclic dione,
.. by a phenyl which itself is substituted at the 4-position by (specifically)
either prop-l-ynyl or
chloroethynyl and at the 2-position by (specifically) methyl or chlorine, or
derivatives of the

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enol ketone tautomer of such cyclic diones, which have herbicidal activity
and/or plant-
growth-inhibiting properties, in particular in the control of grassy
monocotyledonous weeds.
The herbicidal data available, as shown in the Biological Examples
hereinafter, suggests that
these 4-(prop-1-ynyI)-2-(methyl or chloro)-phenyl or 4-(chloroethyny1)-2-
(methyl or chloro)-
phenyl cyclic dione compounds are more potent herbicides against grassy
monocotyledonous weeds (e.g. when applied post-emergence) than the
corresponding 4-
ethyny1-2-(methyl or chloro)-phenyl cyclic dione compounds. The herbicidal
activity against
"warm-season" (warm climate) grassy monocotyledonous weeds of most of the
compounds
of the invention which have been exemplified and tested herein (compounds A-1
to A-17,
A-18 to A-24, P-1 to P-5, or P-7) appears to be potent, in particular after
post-emergence
application of the compounds at an application rate of about 250 g/ha. Also,
many of the
exemplified compounds exhibit a reasonably low phytotoxicity against wheat
and/or certain
docotyledonous crops, in particular soybean and/or sugar beet (see Biological
Examples 1B
and 3 hereinafter).
Therefore, in a first aspect of the present invention, there is provided a
compound of formula
(I):
X
G, R1
3 0
R4
R2
R5 R6
wherein:
X is methyl or chlorine;
R1 is methyl or chlorine;
R2 is hydrogen, methyl, ethyl, n-propyl, cyclopropyl, vinyl, ethynyl,
fluorine, chlorine, bromine,
.. C1-C3alkoxy, 01-C2fluoroalkoxy, 01-C2alkoxy-01-C3alkoxy-, or C1fluoroalkoxy-
C1-C3alkoxY-;
and
R3, R4, R5 and R6, independently of each other, are hydrogen, C1-05alkyl (in
particular C1-
C4alkyl, e.g. Ci-C2alkyl), C2-C4alkenyl (in particular C2-C3alkenyl-CH2-, e.g.
ethenyl-CH2-),
C2-C4alkynyl (in particular C2-C3alkynyl-CH2-, e.g. ethynyl-CH2-), 01-
C2fluoroalkyl,

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C1-C3alkoxyCi-C3alkyl, 01-C3alkylthioC1-C3alkyl, 01-C3alkylsulfinylC1-C3alkyl,
Ci-C3alkylsulfonylC1-C3alkyl; 03-a4cycloalkyl (in particular cyclopropyl); or
an unsubstituted
4, 5 or 6 (e.g. 4 or 5) membered monocyclic heterocyclyl having one ring
heteroatom
independently selected from oxygen, sulfur and nitrogen, and attached at a
ring carbon atom
within the heterocyclyl (in particular tetrahydrofuranyl such as
tetrahydrofuran-3-yl, or
tetrahydropyranyl such as tetrahydropyran-4-y0;
provided that no more than one (in particular none) of R3, R4, R6 and R6 is
alkenyl, alkynyl,
alkoxyalkyl, alkylthioalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl,
cycloalkyl or heterocyclyl;
or R3 and R4 taken together are -(CH2)51- or -(CH2)2-X1-(C1-12)n3- and R5 and
R6 are as
defined herein (e.g. hereinabove), or R6 and R6 taken together
are -(CH2)51- or -(CH2)2-X1-(CH2)3- and R3 and R4 are as defined herein (e.g.
hereinabove);
wherein X1 is 0, S, S(0), S(0)2, NH, N(01-C2alkyl), N(01-C2alkoxy), C(H)(C1-
C2alkyl),
C(C1-C2alky1)2 or C(H)(C1-C2alkoxy);
n1 is 2, 3, 4 or 5 (in particular 4 or 5); and
n2 and n3 are independently 1, 2 or 3 provided that n2 + n3 is 2, 3 or 4 (in
particular 3 or 4);
or R4 and R6 taken together are -(CHAna- or -(CH2)n5-C(R7a)(R7bHCH2)ns- or
wherein R7a is C1-C2alkyl or C1-C2alkoxy; and R7b is hydrogen or C1-C2alkyl
provided that R7b
is hydrogen when R7a is C1-C2alkoxy;
n4 is 1,2 or 3; and
n5 and n6 are independently 0, 1 or 2 provided that n5 + n6 is 0, 1 or 2;
and R7c and R" independently are hydrogen or 01-C2alkyl; and
Y is 0, S, S(0), S(0)2, N(C1-C2alkyl), N(C1-C2alkoxy), C(0), CR8R9or -CR19Rii
K ; and
R8 and R9 are, independently of each other:
hydrogen, C1-C6alkyl (in particular Ci-C4alkyl, e.g. Ci-C2alkyl), C2-C4alkenyl
(in
particular 02-C3alkenyl-CH2-, e.g. ethenyl-CH2-), 02-a4alkynyl (in particular
C2-C3alkynyl-CH2-, e.g. ethynyl-CH2-), C1-C2fluoroalkyl, Ci-C3alkoxyC1-
C3alkyl,
C1-C3alkylthioC1-C3alkyl, 01-C3alkylsulfinylC1-C3alkyl, or 01-
C3alkylsulfonylC1-C3alkyl;
C3-C6cycloalkyl or C3-C6cycloalkyl substituted by one or two substituents
which
independently are C1-C3alkyl (in particular methyl or ethyl) or C1-
C2fluoroalkyl; and in which
one ring CH2 moiety of a 04-C6cycloalkyl is optionally (e.g. preferably)
replaced by an oxygen

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or sulfur atom or by a S(0), S(0)2, NH, N(01-C3alkyl), N(01-C2fluoroalkyl),
N[C(0)01-C3alkyl],
N[C(0)Ci-C2fluoroalkyl] or N(C1-C2alkoxy) moiety;
C3-06cyc1oa1ky1 substituted by one substituent being 01-C3alkoxy (in
particular
C1-C2alkoxy) and optionally further substituted by one substituent being C1-
C2alkyl (in
particular methyl);
05-C6cycloalkenyl or 05-C6cycloalkenyl substituted by one or two 01-C3alkyl
(in
particular methyl) substituents;
C3-C6cycloalkylCi-C2alkyl- (in particular 03-C6cycloalkylmethyl-) or C3-
C6cycloalkylC1-
C2alkyl- (in particular 03-C6cycloalkylmethyl-) substituted by one or two ring
substituents
.. which independently are 01-C3alkyl or 01-C2fluoroalkyl; and in which one
ring CH2 moiety of a
C4-C6cycloalkylC1-C2alkyl- (in particular C4-C6cycloalkylmethyl-) is
optionally (e.g. preferably)
replaced by an oxygen or sulfur atom or by a S(0), S(0)2, NH, N(C1-C2alkyl),
N(01-
C2fluoroalkyl), N[C(0)C1-C3alkyl], N[C(0)Ci-C2fluoroalkyl] or N(C1-C2alkoxy)
moiety;
C3-C6cycloalkylC1-C2alkyl- (in particular 03-C6cycloalkylmethyl-) substituted
by one ring
substituent being C1-C3alkoxy (in particular C1-C2alkoxy) and optionally
further substituted by
one ring substituent being 01-C2alkyl (in particular methyl); or
Het or Het-CH2-, wherein Het is a heteroaryl, attached at a ring-carbon, which
is
optionally substituted by 1,2 or 3 (in particular 1 or 2, e.g. 1) ring-carbon
substituents
independently being 01-C3alkyl (e.g. 01-C2alkyl), C1-C2fluoroalkyl, C1-C3alkyl-
C(0)-,
C1-C2fluoroalkyl-C(0)-, hydroxy (including any oxo tautomer), 02-C3alkenyl
(e.g. ethenyl or
prop-1-enyl), C2-C3alkynyl (e.g. ethynyl or prop-1-ynyl), 01-C3alkoxy (e.g. 01-
C2alkoxy),
C2fluoroalkoxy, halogen (e.g. fluorine or chlorine), cyano or nitro, provided
that any non-
fluorine halogen, alkoxy or fluoroalkoxy is not substituted at any ring-carbon
bonded directly
to a ring-nitrogen of the heteroaryl; and/or, in the case of a 5-membered
heteroaryl ring
containing a ring-nitrogen atom not partaking in a C=N ring double bond, the
heteroaryl is
optionally substituted on the ring-nitrogen atom not partaking in a C=N ring
double bond by
one 01-C3alkyl, 01-C2fluoroalkyl, C1-C3alkyl-C(0)-, C1-C2fluoroalkyl-C(0)- or
Ci-C2alkyl-S(0)2- substituent;
provided that no more than one of R8 and R9 is an optionally substituted
cycloalkyl; an
optionally substituted cycloalkyl in which one ring CH2 moiety has been
replaced by an
oxygen or sulfur atom or by a S(0), S(0)2, NH, N(01-C3alkyl), N(C1-
C2fluoroalkyl),
N[C(0)01-C3alkyl], N[C(0)01-C2fluoroalkyl] or N(01-C2alkoxy) moiety; an
optionally
substituted cycloalkenyl; an optionally substituted cycloalkyl-alkyl-; an
optionally substituted

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cycloalkyl-alkyl- in which one ring CH2 moiety has been replaced by an oxygen
or sulfur atom
or by a S(0), S(0)2, NH, N(Ci-C3alkyl), N(01-02f1u0r0a1ky1), N[C(0)C1-
C3alkyl],
N[C(0)01-C2fluoroalkyl] or N(01-C2alkoxy) moiety; or Het or Het-CH2-;
or R3 is hydrogen or 01-02a1ky1 (in particular H or Me), and R9 is 01-C2alkoxy
(in particular
methoxy);
or R8 and R9 taken together are -(CH2)n7- or -(CH2)ns-X2-(CH2)0-;
wherein X2 is 0, S, S(0), S(0)2, NH, N(01-03a1ky1), N(C1-02f1u0r0a1ky1),
N[C(0)C1-03a1ky1],
N[C(0)01-02f1u0r0a1ky1], N(01-C2alkoxy), C(H)(01-03a1ky1), C(01-02a1ky1)2 or
C(H)(Ci-03a1k0xy);
n7 is 2, 3, 4, 5 or 6 (in particular 4 or 5); and
n8 and n9 are independently 0, 1, 2 or 3 provided that n8 + n9 is 2, 3, 4 or 5
(in particular 3
or 4); and
R19, R11, R12 and R13 are independently of each other hydrogen or Cratalkyl
(in particular
C1-02a1ky1) provided that no more than one of R19, R11, R12 and R13 is C3-
04a1ky1; and
and wherein:
G is hydrogen; an agriculturally acceptable metal, or an agriculturally
acceptable sulfonium or
ammonium group; or
G is -C(Xa)-Ra, -C(Xb)-Xc-Rb, -C(Xd)-N(Rc)-Rd, -S02-Re, -P(Xe)(Rf)-Rg, -CH2-Xf-
Rh; or
phenyl-CH2- or phenyl-CH(C1-C2alkyl)- (in each of which the phenyl is
optionally substituted
by 1, 2 or 3 of, independently, C1-C2alkyl, Cifluoroalkyl, 01-02a1k0xy,
Cifluoroalkoxy, fluorine,
chlorine, bromine, cyano or nitro), or heteroaryl-0H2- or heteroaryl-CH(01-
02a1ky1)- (in each
of which the heteroaryl is optionally substituted by 1, 2 or 3 of,
independently, 01-C2alkyl,
Cifluoroalkyl, 01-02a1koxy, Cifluoroalkoxy, fluorine, chlorine, bromine, cyano
or nitro), or
phenyl-C(0)-0H2- (wherein the phenyl is optionally substituted by 1, 2 or 3
of, independently,
01-C2alkyl, Cifluoroalkyl, 01-C2alkoxy, Cifluoroalkoxy, fluorine, chlorine,
bromine, cyano or
nitro); or 01-06a1k0xy-C(0)-CH2-, 01-C6alkoxy-C(0)-CH=CH-, 02-C7alken-1-yl-0H2-
,
02-C7alken-1-yl-CH(Ci-C2alkyl)-, C2-C4fluoroalken-1-yl-CH2-, 02-C7alkyn-1-yl-
0H2-, or
02-C7alkyn-1-yl-CH(Ci-C2alkyl)-;

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wherein Xa, Xb, Xc, Xd, V and Xf are independently of each other oxygen or
sulfur ( in
particular oxygen); and wherein
Ra is H, C2-
C21alkenyl, 02-C18alkynyl, 01-C10fluoroalkyl, 01-C10cyanoalkyl, C1-
.. Cionitroalkyl, C1-C10aminoalkyl, 01-05alkylamino(C1-05)alkyl, 02-
C8dialkylamino(C1-05)alkyl,
C3-C7cycloalkyl(Ci-05)alkyl, Ci-05alkoxy(Ci-05)alkyl, C3-05alkenyloxy(C1-
05)alkyl, C3-
05alkynyloxy (C1-05)alkyl, C1-05alkylthio(C1-05)alkyl, C1-05alkylsulfinyl(C1-
05)alkyl, Cr
C5alkylsulfonyl(Ci-05)alkyl, C2-C8alkylideneaminoxy(C1-05)alkyl, Ci-
05alkylcarbonyl(Ci-
05)alkyl, C1-05alkoxycarbonyl(C1-05)alkyl, aminocarbonyl(C1-05)alkyl, C1-
C5alkylaminocarbonyl(C1-05)alkyl, C2-C8dialkylaminocarbonyl(C1-05)alkyl,
C5alkylcarbonylamino(C1-05)alkyl, N-(C1-05)alkylcarbonyl-N-(C1-
05)alkylamino(C1-05)alkyl,
C3-C6trialkylsilyl(C1-05)alkyl, phenyl(01-05)alkyl (wherein the phenyl is
optionally substituted
by 1, 2 or 3 of, independently, C1-C3alkyl, C1-C3fluoroalkyl, 01-C3alkoxy, C1-
C3fluoroalkoxy,
C1-C3alkylthio, C1-C3alkylsulfinyl, C1-C3alkylsulfonyl, halogen, cyano, or
nitro), heteroaryl(C1-
C5)alkyl (wherein the heteroaryl is optionally substituted by 1, 2 or 3 of,
independently, C1-
C3alkyl, 01-C3fluoroalkyl, C1-C3alkoxy, C1-C3fluoroalkoxy, C1-C3alkylthio, C1-
C3alkylsulfinyl,
C1-C3alkylsulfonyl, halogen, cyano, or nitro), C2-05fluoroalkenyl, C3-
C8cycloalkyl; phenyl or
phenyl substituted by 1, 2 or 3 of, independently, C1-C3alkyl, C1-
C3fluoroalkyl, C1-C3alkoxy,
Ci-C3fluoroalkoxy, halogen, cyano or nitro; or heteroaryl or heteroaryl
substituted by 1, 2 or 3
of, independently, C1-C3 alkyl, C1-C3fluoroalkyl, C1-C3alkoxy, C1-
C3fluoroalkoxy, halogen,
cyano or nitro;
Rb is C1-C13alkyl, C3-C18alkenyl, C3-C13alkynyl, C2-C10fluoroalkyl, C1-
C10cyanoalkyl, C1
Cionitroalkyl, C2-C10aminoalkyl, 01-05alkylamino(C1-05)alkyl, C2-
C8dialkylamino(C1-05)alkyl,
C3-C7cycloalkyl(C1-05)alkyl, C1-05alkoxy(C1-05)alkyl, C3-05alkenyloxy(C1-
05)alkyl, C3-
05alkynyloxy(C1-05)alkyl, C1-05alkylthio(01-05)alkyl, C1-05alkylsulfinyl(C1-
05)alkyl, C1-
05alkylsulfonyl(C1-05)alkyl, 02-C8alkylideneaminoxy(C1-05)alkyl, C1-
05alkylcarbonyl(C1-
05)alkyl, C1-05alkoxycarbonyl(C1-05)alkyl, aminocarbonyl(C1-05)alkyl, Cr
C5alkylaminocarbonyl(Ci-05)alkyl, C2-C8dialkylaminocarbonyl(C1-05)alkyl, C1-
C5alkylcarbonylamino(C1-05)alkyl, N-(Ci-05)alkylcarbonyl-N-(Ci-
05)alkylamino(C1-05)alkyl,
C3-C6trialkylsilyl(Ci-05)alkyl, phenyl(C1-05)alkyl (wherein the phenyl is
optionally substituted
by 1, 2 or 3 of, independently, C1-C3alkyl, C1-C3fluoroalkyl, C1-C3alkoxy, C1-
C3fluoroalkoxy,
Ci-C3alkylthio, C1-C3alkylsulfinyl, C1-C3alkylsulfonyl, halogen, cyano, or
nitro), heteroarylCi-
05alkyl (wherein the heteroaryl is optionally substituted by 1, 2 or 3 of,
independently, Cr

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C3alkyl, 01-C3fluoroalkyl, C1-C3alkoxy, 01-C3fluoroalkoxy, C1-C3alkyl-thio, 01-
C3alkylsulfinyl,
Ci-C3alkylsulfonyl, halogen, cyano, or nitro), C3-05fluoroalkenyl, C3-
C8cycloalkyl; phenyl or
phenyl substituted by 1, 2 or 3 of, independently, 01-C3alkyl, 01-
C3fluoroalkyl, C1-C3alkoxy,
C1-C3fluoroalkoxy, halogen, cyano or nitro; or heteroaryl or heteroaryl
substituted by 1, 2 or 3
.. of, independently, C1-03 alkyl, C1-C3fluoroalkyl, 01-C3alkoxy, C1-
C3fluoroalkoxy, halogen,
cyano or nitro; and
IR' and Rd are each independently of each other hydrogen, C1-Cioalkyl, C3-
Ci0alkenyl, C3-
C10alkynyl, C2-C10fluoroalkyl, 01-C10cyanoalkyl, C1-C10nitroalkyl,
CrCioaminoalkyl,
C5alkylamino(01-05)alkyl, 02-C8dialkylamino(C1-05)alkyl, 03-C7cycloalkyl(01-
05)alkyl, C1-
05alkoxy(C1-05)alkyl, C3-05alkenyloxy(C1-05)alkyl, C3-05alkynyloxy(C1-
05)alkyl,
C5alkylthio(C1-05)alkyl, C1-05alkylsulfinyl(C1-05)alkyl, C1-05alkylsulfonyl(01-
05)alkyl, 02-
C8a lkyliden ea mi noxy(Ci-05)a lkyl, C1-05alkylcarbonyl(C1-05)alkyl, 01-
05alkoxycarbonyl(01-
05)alkyl, aminocarbonyl(C1-05)alkyl, C1-05alkylaminocarbonyl(C1-05)alkyl, C2-
C8dialkylaminocarbonyl(01-05)alkyl, C1-05alkylcarbonylamino(C1-05)alkyl, N-(C1-
05)alkylcarbonyl-N-(02-05)alkylaminoalkyl, C3-C6trialkylsilyl(01-05)alkyl,
phenyl(01-05)alkyl
(wherein the phenyl is optionally substituted by 1, 2 or 3 of, independently,
01-C3alkyl, C1-
C3fluoroalkyl, 01-C3alkoxy, C1-C3fluoroalkoxy, 01-C3alkylthio, 01-
C3alkylsulfinyl, Ci-
C3alkylsulfonyl, halogen, cyano, or nitro), heteroaryl(C1-05)alkyl (wherein
the heteroaryl is
optionally substituted by 1, 2 or 3 of, independently, 01-C3alkyl, 01-
C3fluoroalkyl, C1-
C3alkoxy, C1-C3fluoroalkoxy, 01-C3alkylthio, 01-C3alkylsulfinyl, C1-
C3alkylsulfonyl, halogen,
cyano, or nitro), C2-05fluoroalkenyl, C3-C8cycloalkyl; phenyl or phenyl
substituted by 1, 2 or 3
of, independently, C1-03a1ky1, 01-C3fluoroalkyl, C1-C3alkoxy, 01-
C3fluoroalkoxy, halogen,
cyano or nitro; heteroaryl or heteroaryl substituted by 1, 2 or 3 of,
independently, C1-C3alkyl,
C1-C3fluoroalkyl, C1-C3alkoxy, C1-C3fluoroalkoxy, halogen, cyano or nitro;
heteroarylamino or
heteroarylamino substituted by 1, 2 or 3 of, independently, 01-C3alkyl, 01-
C3fluoroalkyl, Ci-
C3alkoxy, C1-C3fluoroalkoxy, halogen, cyano or nitro; diheteroarylamino or
diheteroarylamino
substituted by 1, 2 or 3 of, independently, C1-C3alkyl, C1-C3fluoroalkyl, C1-
C3alkoxy, C1-
C3fluoroalkoxy, halogen, cyano or nitro; phenylamino or phenylamino
substituted by 1, 2 or 3
of, independently, Ci-C3alkyl, C1-C3fluoroalkyl, C1-C3alkoxy, C1-
C3fluoroalkoxy, halogen,
cyano or by nitro; diphenylamino or diphenylamino substituted by 1, 2 or 3 of,
independently,
C1-C3alkyl, C1-C3fluoroalkyl, 01-C3alkoxy, C1-C3fluoroalkoxy, halogen, cyano
or nitro; or C3-
C7cycloalkylamino, di(C3-C7cycloalkyl)amino or 03-C7cycloalkoxy;

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or Rc and Rd, together with the nitrogen to which they are bonded, to form an
unsubstituted 4,
5, 6 or 7 (e.g. 5 or 6) membered ring, optionally containing one heteroatom
selected from 0
or S; and
Re is C1-C1oalkyl, 02-C1oalkenyl, 02-C1oalkynyl, Crawfluoroalkyl, Ci-
Clocyanoalkyl,
Cionitroalkyl, C1-C1oaminoalkyl, Ci-05alkylamino(Ci-05)alkyl, C2-
C8dialkylamino(Ci-05)alkyl,
C3-C7cycloalkyl(C1-05)alkyl, C1-05alkoxy(C1-05)alkyl, C3-05alkenyloxy(C1-
05)alkyl, 03-
05alkynyloxy(Ci-05)alkyl, C1-05alkylthio(C1-05)alkyl, Ci-05alkylsulfinyl(Ci-
05)alkyl, C1-
05alkylsulfonyl(C1-05)alkyl, 02-C8alkylideneaminoxy(C1-05)alkyl, 01-
05alkylcarbonyl(01-
C5)alkyl, C1-05alkoxycarbonyl(C1-05)alkyl, aminocarbonyl(01-05)alkyl, Ci-
05alkylaminocarbonyl(C1-05)alkyl, C2-C8dialkylaminocarbonyl(C1-05)alkyl, C1-
05alkylcarbonylamino(01-05)alkyl, N-(01-05)alkylcarbonyl-N-(01-
05)alkylamino(01-05)alkyl,
C3-C8trialkylsilyl(01-05)alkyl, phenyl(01-05)alkyl (wherein the phenyl is
optionally substituted
by 1, 2 or 3 of, independently, C1-C3alkyl, C1-C3fluoroalkyl, C1-C3alkoxy, C1-
C3fluoroalkoxy,
C1-C3alkylthio, 01-C3alkylsulfinyl, 01-C3alkylsulfonyl, halogen, cyano, or
nitro), heteroaryl(C1-
05)alkyl (wherein the heteroaryl is optionally substituted by 1, 2 or 3 of,
independently, Cr
C3alkyl, 01-C3fluoroalkyl, C1-C3alkoxy, 01-C3fluoroalkoxy, C1-C3alkylthio, C1-
C3alkylsulfinyl,
C1-C3alkylsulfonyl, halogen, cyano, or nitro), C2-05fluoroalkenyl, C3-
C8cycloalkyl; phenyl or
phenyl substituted by 1, 2 or 3 of, independently, C1-C3alkyl, Ci-
C3fluoroalkyl, C1-C3alkoxy,
C1-C3fluoroalkoxy, halogen, cyano or nitro; heteroaryl or heteroaryl
substituted by 1, 2 or 3 of,
independently, C1-C3alkyl, C1-C3fluoroalkyl, C1-C3alkoxy, C1-C3fluoroalkoxy,
halogen, cyano
or nitro; heteroarylamino or heteroarylamino substituted by 1, 2 or 3 of,
independently, C1-C3
alkyl, C1-C3fluoroalkyl, C1-C3alkoxy, C1-C3fluoroalkoxy, halogen, cyano or
nitro;
diheteroarylamino or diheteroarylamino substituted by 1, 2 or 3 of,
independently, C1-C3alkyl,
C1-C3fluoroalkyl, C1-C3alkoxy, C1-C3fluoroalkoxy, halogen, cyano or nitro;
phenylamino or
phenylamino substituted by 1, 2 or 3 of, independently, 01-C3alkyl, C1-
C3fluoroalkyl, Ci-
C3alkoxy, C1-C3fluoroalkoxy, halogen, cyano or nitro; diphenylamino or
diphenylamino
substituted by 1, 2 or 3 of, independently, 01-C3alkyl, C1-C3fluoroalkyl, C1-
C3alkoxy, C1-
C3fluoroalkoxy, halogen, cyano or nitro; or 03-C7cycloalkylamino, di(03-
C7cycloalkyl)amino,
03-C7cycloalkoxy, C1-C1oalkoxy, Ci-Ciofluoroalkoxy, C1-05alkylamino or
di(Cratalkyl)amino;
Rf and Rg are are each independently of each other 01-C10alkyl, C2-C10alkenyl,
C2-C10alkynyl,
Ci-Cioalkoxy, CrCiofluoroalkyl, Ci-Ciocyanoalkyl, CrCionitroalkyl, C1-
C1oaminoalkyl,
C5alkylamino(Ci-05)alkyl, 02-C8dialkylamino(C1-05)alkyl, 03-C7cycloalkyl(C1-
05)alkyl,

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C5a I koxy(C -05)a I kyl, 03-05alkenyloxy(01-05)alkyl, 03-05alkynyloxy(C1-
05)alkyl, C1-
05alkylthio(01-05)alkyl, C1-05alkylsulfinyl(C1-05)alkyl, 01-05alkylsulfonyl(01-
05)alkyl, 02-
C8alkylideneaminoxy(Ci-05)alkyl, Ci-05alkylcarbonyl(Ci-05)alkyl, Ci-
05alkoxycarbonyl(Ci-
05)alkyl, aminocarbonyl(C1-05)alkyl, 01-05alkylaminocarbonyl(01-05)alkyl, C2-
C8dialkylaminocarbonyl(Ci-05)alkyl, C1-05alkylcarbonylamino(01-05)alkyl, N-(01-
05)alkylcarbonyl-N-(02-05)alkylaminoalkyl, 03-C6trialkylsilyl(Ci-05)alkyl,
phenyl(Ci-05)alkyl
(wherein the phenyl is optionally substituted by 1, 2 or 3 of, independently,
01-03a1ky1, C1-
C3fluoroalkyl, C1-C3alkoxy, C1-C3fluoroalkoxy, C1-C3alkylthio, C1-
C3alkylsulfinyl, 01-
C3alkylsulfonyl, halogen, cyano, or nitro), heteroaryl(C1-05)alkyl (wherein
the heteroaryl is
optionally substituted by 1, 2 or 3 of, independently, 01-C3alkyl, 01-
C3fluoroalkyl,
C3alkoxy, C1-C3fluoroalkoxy, C1-C3alkylthio, C1-C3alkylsulfinyl, C1-
C3alkylsulfonyl, halogen,
cyano, or nitro), 02-05fluoroalkenyl, 03-C3cycloalkyl; phenyl or phenyl
substituted by 1, 2 or 3
of, independently, C1-C3alkyl, 01-C3fluoroalkyl, 01-C3alkoxy, 01-
C3fluoroalkoxy, halogen,
cyano or nitro; heteroaryl or heteroaryl substituted by 1, 2 or 3 of,
independently, C1-03 alkyl,
C1-C3fluoroalkyl, 01-C3alkoxy, C1-C3fluoroalkoxy, halogen, cyano or nitro;
heteroarylamino or
heteroarylamino substituted by 1, 2 or 3 of, independently, 01-03 alkyl, C1-
C3fluoroalkyl, C1-
C3alkoxy, C1-C3fluoroalkoxy, halogen, cyano or nitro; diheteroarylamino or
diheteroarylamino
substituted by 1, 2 or 3 of, independently, C1-C3 alkyl, C1-C3fluoroalkyl, 01-
C3alkoxy, C1-
C3fluoroalkoxy, halogen, cyano or nitro; phenylamino or phenylamino
substituted by 1, 2 or 3
of, independently, C1-C3alkyl, C1-C3fluoroalkyl, 01-C3alkoxy, 01-
C3fluoroalkoxy, halogen,
cyano or nitro; diphenylamino or diphenylamino substituted by 1, 2 or 3 of,
independently, Ci-
C3alkyl, C1-C3fluoroalkyl, C1-C3alkoxy, C1-C3fluoroalkoxy, halogen, cyano or
nitro; or C3-
C7cycloalkylamino, di(C3-C7cycloalkyl)amino, C3-C7cycloalkoxy, 01-
C10fluoroalkoxy, C1-
05alkylamino or di(01-C4alkyl)amino; or benzyloxy or phenoxy, wherein the
benzyl and
phenyl groups are in turn optionally substituted by 1, 2 or 3 of,
independently, 01-C3alkyl,
C3fluoroalkyl, 01-C3alkoxy, C1-C3fluoroalkoxy, halogen, cyano or nitro; and
Rh is 03-Cioalkenyl, Ci-Ciofluoroalkyl, Ci-Ciocyanoalkyl,
Cionitroalkyl, 02-010am1n0a1ky1, 01-05alkylamino(Ci-05)alkyl, 02-
C8dialkylamino(01-05)alkyl,
03-07cyc10a1ky1(Ci-05)alkyl, Ci-05a1k0xy(Ci-05)alkyl, 03-05a1keny10xy(Ci-
05)alkyl, 03-
05alkynyloxy(Ci-05)alkyl, 01-05alkylthio(01-05)alkyl, Ci-05alkylsulfinyl(Ci-
05)alkyl,
C5alkylsulfonyl(01-05)alkyl, 02-C8alkylideneaminoxy(C1-05)alkyl, 01-
05alkylcarbonyl(01-
05)alkyl, 01-05alkoxycarbonyl(C1-05)alkyl, aminocarbonyl(01-05)alkyl, Cr
C5alkylaminocarbonyl(Ci-05)alkyl, C2-C8dialkylaminocarbonyl(Ci-05)alkyl,

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C5alkylcarbonylamino(Ci-05)alkyl, N-(01-05)alkylcarbonyl-N-(01-
05)alkylamino(01-05)alkyl,
C3-C6trialkylsilyl(Ci-05)alkyl, phenyl(Ci-05)alkyl (wherein the phenyl is
optionally substituted
by 1, 2 or 3 of, independently, C1-C3alkyl, 01-C3fluoroalkyl, 01-C3alkoxy, 01-
C3fluoroalkoxy,
C1-C3alkylthio, 01-C3alkylsulfinyl, 01-03 alkylsulfonyl, halogen, cyano or
nitro), heteroaryl(01-
C5)alkyl (wherein the heteroaryl is optionally substituted by 1, 2 or 3 of,
independently, Cr
C3alkyl, 01-03f1u0r0a1ky1, C1-03a1k0xy, C1-03f1uoroa1koxy, C1-C3alkylthio, 01-
03a1ky1su1finy1,
C1-03 alkylsulfonyl, halogen, cyano or nitro), phenoxy(C1-05)alkyl (wherein
the phenyl is
optionally substituted by 1, 2 or 3 of, independently, C1-C3alkyl, C1-
C3fluoroalkyl, C1-
C3alkoxy, C1-C3fluoroalkoxy, 01-C3alkylthio, 01-C3alkylsulfinyl, Ci-03
alkylsulfonyl, halogen,
.. cyano or nitro), heteroaryloxy(C1-05)alkyl (wherein the heteroaryl is
optionally substituted by
1, 2 or 3 of, independently, C1-C3alkyl, C1-C3fluoroalkyl, C1-C3alkoxy, C1-
C3fluoroalkoxy, C1-
C3alkylthio, C1-C3alkylsulfinyl, 01-03 alkylsulfonyl, halogen, cyano or
nitro), C3-
05fluoroalkenyl, 03-C8cycloalkyl; phenyl or phenyl substituted by 1, 2 or 3
of, independently,
C1-C3alkyl, C1-C3fluoroalkyl, 01-C3alkoxy, C1-C3fluoroalkoxy, halogen, cyano
or nitro;
heteroaryl or heteroaryl substituted by 1, 2 or 3 of, independently, 01-
C3alkyl, Ci-
C3fluoroalkyl, 01-C3alkoxy, C1-C3fluoroalkoxy, halogen, cyano or nitro; 01-
C6alkyl-C(0)-; or
phenyl-C(0)- wherein the phenyl is optionally substituted by 1 or 2 of,
independently, C1-
C2alkyl, Cifluoroalkyl, 01-C2alkoxy, Cifluoroalkoxy, fluorine, chlorine,
bromine, cyano or nitro;
wherein "heteroaryl" means an aromatic ring system containing at least one
ring heteroatom
and consisting either of a single ring or of two fused rings;
and wherein the compound of formula (I) is optionally present (e.g. where
chemically
possible) as an agrochemically acceptable salt thereof.
In the substituent definitions of the compounds of the formula I, each alkyl
moiety either
alone or as part of a larger group (such as alkoxy, alkylthio, alkoxycarbonyl,
alkylcarbonyl,
alkylaminocarbonyl, or dialkylaminocarbonyl, et al.) can be straight-chained
or branched.
Typically, the alkyl is, for example, methyl, ethyl, n-propyl, isopropyl, n-
butyl, sec-butyl,
isobutyl, tert-butyl, n-pentyl, neopentyl, or n-hexyl. The alkyl groups can
e.g. be 01-C6alkyl
groups (except where already defined more narrowly), but are preferably
Cratalkyl or Cr

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C3alkyl groups (except where already defined more narrowly), and, more
preferably, are
Ci-C2alkyl groups such as methyl.
Alkenyl and alkynyl moieties can be in the form of straight or branched
chains, and the
alkenyl moieties, where appropriate, can be of either the (E)- or (Z)-
configuration. The
alkenyl or alkynyl are typically C2-C3alkenyl or 02-C3alkynyl such as vinyl,
ally!, ethynyl,
propargyl or prop-1-ynyl. Alkenyl and alkynyl moieties can contain one or more
double
and/or triple bonds in any combination; but preferably contain only one double
bond (for
alkenyl) or only one triple bond (for alkynyl).
Halogen is fluorine, chlorine, bromine or iodine. Preferred halogens are
fluorine, chlorine or
bromine.
Fluoroalkyl groups are alkyl groups which are substituted with one or more
(e.g. 1, 2, 3, 4 or
5; in particular 1, 2 or 3; e.g. 1 or 2) fluorine atoms. Fluoroalkyl is
typically C1-C3fluoroalkyl or
C1-02f1u0r0a1ky1 (preferably Cifluoroalkyl), such as CF3, CH F2, CH2F, CH3CHF-
, CF3CH2-,
CHF2CH2-, CH2FCH2-, CHF2CF2- or (CH3)20E-. Fluoroalkoxy is typically C1-
03f1uoroa1koxy
or C1-C2fluoroalkoxy (preferably Cifluoroalkoxy), such as CF30, CHF20, CH2F0,
CH3CHF0-,
CF3CH20-, CHF2CH20- or CH2FCH20-.
In the context of the present specification the term "aryl" means phenyl or
naphthyl. A
preferred aryl group is phenyl.
The term "heteroaryl" as used herein means an aromatic ring system containing
at least one
ring heteroatom and consisting either of a single ring or of two fused rings.
Preferably, single
rings will contain 1, 2 or 3 ring heteroatoms and bicyclic systems 1, 2, 3 or
4 ring
heteroatoms which will preferably be selected from nitrogen, oxygen and
sulfur. Typically, a
"heteroaryl" is fury!, thienyl, pyrrolyl, pyrazolyl, imidazolyl, 1,2,3-
triazolyl, 1,2,4-triazolyl,
oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2,4-oxadiazolyl, 1,3,4-
oxadiazolyl,
1,2,5-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl,
1,2,5-thiadiazolyl,
pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, 1,2,3-triazinyl, 1,2,4-
triazinyl, 1,3,5-triazinyl,
benzofuryl, benzisofuryl, benzothienyl, benzisothienyl, indolyl, isoindolyl,
indazolyl,
benzothiazolyl, benzisothiazolyl, benzoxazolyl, benzisoxazolyl,
benzimidazolyl, 2,1,3-

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benzoxadiazole, quinolinyl, isoquinolinyl, cinnolinyl, phthalazinyl,
quinazolinyl, quinoxalinyl,
naphthyridinyl, benzotriazinyl, purinyl, pteridinyl or indolizinyl; optionally
present, where
chemically possible, as an agrochemically acceptable salt thereof.
The term "heterocyclyl" as used herein, except where explicitly stated
otherwise, means a 4,
5, 6 or 7 (in particular 5, 6 or 7) membered monocyclic organic ring or a 8,
9, 10 or 11 (in
particular 8, 9 or 10) membered fused bicyclic organic ring system, which is
fully saturated,
and which has one or two (preferably one) ring heteroatoms independently
selected from
oxygen, sulfur and nitrogen. Where the heterocyclyl has two ring heteroatoms,
preferably,
the two ring heteroatoms are separated by at least two ring carbon atoms.
Preferably, the
heterocyclyl is attached at a ring carbon atom within the heterocyclyl. In
particular, the
heterocyclyl can be tetrahydrofuranyl, tetrahydropyranyl,
tetrahydrothiophenyl, 1,4-dioxanyl,
1,4-dithianyl, morpholinyl, thiomorpholinyl, pyrrolidinyl, piperidinyl or
piperazinyl; more
particularly tetrahydrofuranyl (e.g. tetrahydrofuran-2-y1 or particularly
tetrahydrofuran-3-y1),
tetrahydropyranyl (e.g. tetrahydropyran-2-yl, tetrahydropyran-3-y1 or
particularly
tetrahydropyran-4-y1), morpholinyl, pyrrolidinyl (e.g. pyrrolidin-2-y1 or
particularly pyrrolidin-3-
yl), piperidinyl (e.g. piperidin-2-yl, piperidin-3-y1 or particularly
piperidin-4-y1) or piperazinyl. In
a particular embodiment, the heterocyclyl, when optionally substituted, is
optionally
substituted by 1 or 2 (e.g. 1) ring-carbon substituents independently being C1-
C3alkyl (e.g.
C1-C2alkyl), C1-C2fluoroalkyl or oxo (=0), and/or is optionally substituted by
one C1-C3alkyl
(e.g. C1-C2alkyl), 01-C2fluoroalkyl or C1-C3alkoxy (e.g. 01-C2alkyl or C1-
C2fluoroalkyl)
substituent on a ring nitrogen if present, and/or is optionally substituted by
one or two oxo
(=0) substituents on a ring sulfur if present.
Preferably, a cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl or
cyclohexyl. (Cycloalkyl)alkyl
is preferably (cycloalkyl)methyl such as (C3-C6cycloalkyl)methyl in particular
cyclopropylmethyl. Preferably, cycloalkenyl is cyclopentenyl or cyclohexenyl.
The invention relates also to the agriculturally acceptable salts which the
compounds of
formula I are able to form with transition metal, alkali metal and alkaline
earth metal bases,
amines, quaternary ammonium bases or tertiary sulfonium bases.

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Among the transition metal, alkali metal and alkaline earth metal salt
formers, special
mention should be made of the hydroxides of copper, iron, lithium, sodium,
potassium,
magnesium and calcium, and preferably the hydroxides, bicarbonates and
carbonates of
sodium and potassium. Accordingly, in one particular embodiment of the
invention, G is an
.. agriculturally acceptable metal such as copper, iron, lithium, sodium,
potassium, magnesium
or calcium (more particularly an agriculturally acceptable alkali metal or
alkaline earth metal).
Examples of amines suitable for ammonium salt formation include ammonia as
well as
primary, secondary and tertiary CrCisalkylamines, Crathydroxyalkylamines and
C2-C4alkoxyalkyl-amines, for example methylamine, ethylamine, n-propylamine,
isopropylamine, the four butylamine isomers, n-amylamine, isoamylamine,
hexylamine,
heptylamine, octylamine, nonylamine, decylamine, pentadecylamine,
hexadecylamine,
heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine,
methylhexylamine, methylnonylamine, methylpentadecylamine,
methyloctadecylamine,
ethylbutylamine, ethylheptylamine, ethyloctylamine, hexylheptylamine,
hexyloctylamine,
dimethylamine, diethylamine, di-n-propylamine, di-isopropylamine, di-n-
butylamine, di-n-
amylamine, di-isoamylamine, dihexylamine, diheptylamine, dioctylamine,
ethanolamine, n-
propanolamine, isopropanolamine, N,N-diethanolamine, N-ethylpropanolamine, N-
butylethanolamine, allylamine, n-but-2-enylamine, n-pent-2-enylamine, 2,3-
dimethylbut-2-
.. enylamine, dibut-2-enylamine, n-hex-2-enylamine, propylenediamine,
trimethylamine,
triethylamine, tri-n-propylamine, tri-isopropylamine, tri-n-butylamine, tri-
isobutylamine, tri-sec-
butylamine, tri-n-amylamine, methoxyethylamine and ethoxyethylamine;
heterocyclic amines,
for example pyridine, quinoline, isoquinoline, morpholine, piperidine,
pyrrolidine, indoline,
quinuclidine and azepine; primary arylamines, for example anilines,
methoxyanilines,
ethoxyanilines, o-, m- and p-toluidines, phenylenediamines, benzidines,
naphthylamines and
o-, m- and p-chloroanilines; but especially triethylamine, isopropylamine and
di-
isopropylamine. Accordingly, in one particular embodiment of the invention, G
is an
agriculturally acceptable ammonium group, wherein the compound of formula (I)
is an
ammonium salt formed from: ammonia, a primary, secondary or tertiary C1-
C18alkylamine, a
Crathydroxyalkylamine, or a 02-C4alkoxyalkyl-amine.
Preferred quaternary ammonium bases suitable for salt formation correspond,
for example,
to the formula [N(Raa Rbb Rcc rC r-scich]
H , wherein Raa, Rbb, Rcc and rc r-scid
are each independently of
the others hydrogen or Cratalkyl. Further suitable tetraalkylammonium bases
with other

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anions can be obtained, for example, by anion exchange reactions. Accordingly,
in one
particular embodiment of the invention, G is an agriculturally acceptable
ammonium group,
wherein the compound of formula (I) is a salt formed from a quaternary
ammonium base of
formula [N(Raa Rbb Rcc
UN wherein Raa,
Rcc and Rdd are each independently of the
others hydrogen or C1-C4alkyl.
Preferred tertiary sulfonium bases suitable for salt formation correspond, for
example, to the
formula [SReeRffR9OH, wherein Ree, Rif and IR are each independently of the
others C1-C4
alkyl. Trimethylsulfonium hydroxide is especially preferred. Suitable
sulfonium bases may be
obtained from the reaction of thioethers, in particular dialkylsulfides, with
alkylhalides,
followed by conversion to a suitable base, for example a hydroxide, by anion
exchange
reactions. Accordingly, in one particular embodiment of the invention, G is an
agriculturally
acceptable sulfonium group, wherein the compound of formula (I) is a salt
formed from a
tertiary sulfonium base of formula [SR"RffR990H, wherein R", Rif and R99 are
each
independently of the others C1-04 alkyl.
It should be understood that in those compounds of formula I, where G is a
metal,
ammonium group or sulfonium group as mentioned above, and as such represents a
cation,
the corresponding negative charge is largely delocalised across the 0-C=C-C=0
unit within
formula (I).
The compounds of formula I according to the invention also include hydrates
which may be
formed during the salt formation.
When G is -C(X8)-Re, -C(Xb)-Xc-Rb, -C(Xd)-N(Rc)-Rd, -S02-Re, -P(Xe)(R5-R9, -
CH2-Xf-Rh; or
phenyl-CH2- or phenyl-CH(C1-C2alkyl)- (in each of which the phenyl is
optionally substituted),
or heteroaryl-CH2- or heteroaryl-CH(C1-C2alkyl)- (in each of which the
heteroaryl is optionally
substituted), or phenyl-C(0)-CH2- (wherein the phenyl is optionally
substituted); or
C1-C6alkoxy-C(0)-CH2-, C1-C6alkoxy-C(0)-CH=CH-, C2-C7alken-1-yl-CH2-, C2-
C7alken-1-
yl-CH(C1-C2alkyl)-, C2-C4fluoroalken-1-yl-CH2-, C2-C7alkyn-1-yl-CH2-, or C2-
C7alkyn-1-yl-
CH(Ci-C2alkyl)-; generally these G groups are latentiating groups (i.e.
leaving or removeable
groups), which are generally selected to allow their removal, typically by one
or a
combination of biochemical, chemical or physical processes, to afford the
corresponding
compound of formula (I) where G is H, before, during or following (preferably
during or
following, more preferably following) application of the compound of formula
(I) to the treated

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area (e.g. field) or to plants. Examples of these processes include enzymatic
cleavage or
other in/on-plant cleavage (e.g. cleavage of ester and/or carbonate moieties),
chemical
hydrolysis, and/or photoloysis. Some compounds bearing such groups G
occasionally offer
certain advantages or different technical properties, such as improved and/or
more
consistent and/or different penetration of the cuticula of the plants treated,
increased and/or
different tolerance of certain crops, improved and/or different compatibility
or stability in
formulated mixtures containing other herbicides, herbicide safeners, plant
growth regulators,
fungicides or insecticides, or reduced and/or different leaching properties in
soils.
The preferred, suitable and/or particular values of the substituents in or
other features of the
compound of formula (I), in particular G, X, R1, R2, R2A, R2B, R2c, R3, Ra,
R5, R6, R7, R8, R9,
R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, Ra, Rb,
Rc, Rd, Re, Rf, Rg, Rh,
xa, xb, xc, xd, xe, xf,
U Het, X1, n1, n2 and/or n3, are set out below (and/or generally herein),
and can be either taken alone or taken together with one or more of any other
preferred,
suitable and/or particular features in any combination(s) thereof. In this
paragraph,
"preferred" is intended to encompass more preferred, even or still or yet more
preferred,
particularly or highly preferred, most preferred and all similar terms.
In a particular embodiment, G is hydrogen; an agriculturally acceptable metal
(e.g. an
agriculturally acceptable alkali metal or alkaline earth metal, e.g. lithium,
sodium, potassium,
magnesium or calcium), or an agriculturally acceptable sulfonium or ammonium
group; or G
is _c(xa)-Ra, _c(x13) 2,c_
Rb or -S02-R5, wherein Xa, Ra, xb,
Rb and Re are as defined herein.
In one preferred embodiment, G is hydrogen; an agriculturally acceptable metal
(e.g. an
agriculturally acceptable alkali metal or alkaline earth metal, e.g. lithium,
sodium, potassium,
magnesium or calcium), or an agriculturally acceptable sulfonium or ammonium
group; or G
is -C(X8)-Ra or -C( ) A wherein Xa, Ra, Xb, Xc and Rb are as defined
herein.
In a particular embodiment, G is a group -C(Xa)-Ra or -C )cR
wherein Xa,
(xbs_x,A _b, Ra,
xb, xc
and Rb are as defined herein.
Preferably, Xa, bx xc, s,c1,
Xe and/or Xf are oxygen. Alternatively, preferably, Xc is sulfur.
More preferably, Xa, bx , ¨c
X Xd, Xe and Xf are oxygen.

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Preferably, Ra is C1-C1oalkyl (e.g. Ci-C6alkyl), 02-C6alkenyl (e.g. C2-
C4alkenyl), 02-C6alkynyl
(e.g. C2-C4alkynyl), 03-C6cycloalkyl or 01-C4alkoxyC1-C4alkyl. Alternatively,
preferably, Ra is
C3-C7cycloalkyl(C1-05)alkyl, or phenyl or phenyl substituted by 1, 2 or 3 of,
independently, C-
C3alkyl, C1-C3fluoroalkyl, Ci-C3alkoxy, C1-C3fluoroalkoxy, halogen, cyano or
nitro.
Preferably, Rb is Cl-Cioalkyl (e.g. C1-C6alkyl), 02-05alkenyl-CH2- (e.g. 02-
C3alkenyl-CH2-),
C2-C4alkenyl-CH(Me)- (e.g. C2-C3alkenyl-CH(Me)-), C2-05alkynyl-CH2- (e.g.
C2-C3alkynyl-CH2-), C2atalkynyl-CH(Me)- (e.g. 02-C3alkynyl-CH(Me)-), C3-
C6cycloalkyl or
CratalkoxyCratalkyl. Alternatively, preferably, Rb is 03-C7cycloalkyl(01-
05)alkyl, or phenyl
or phenyl substituted by 1, 2 or 3 of, independently, C1-C3alkyl, C1-
C3fluoroalkyl, C1-C3alkoxy,
C1-C3fluoroalkoxy, halogen, cyano or nitro.
Preferably, Re is C1-C10alkyl (e.g. C1-C6alkyl or C1-C4alkyl) or C1-
C10fluoroalkyl (e.g. C1-
C3fluoroalkyl). In particular, Re is C1-C10alkyl (e.g. 01-C6alkyl or 01-
C4alkyl).
When G is -C(V)-1:25 or -C(Xb)-Xc-Rb, then preferably Xa, Xb and Xc are
oxygen, Ra is Cr
Cioalkyl (e.g. C1-C6alkyl), 02-C6alkenyl (e.g. 02-C4alkenyl), 02-C6alkynyl
(e.g. C2-C4alkynyl),
C3-C6cycloalkyl or C1atalkoxyCi-atalkyl; and Rb is C1-C1oalkyl (e.g. C1-
C6alkyl),
C2-05alkenyl-CH2- (e.g. C2-C3alkenyl-CH2-), C2-C4alkenyl-CH(Me)- (e.g.
C2-C3alkenyl-CH(Me)-), 02-05alkynyl-CH2- (e.g. 02-C3alkynyl-CH2-),
C2-C4alkynyl-CH(Me)- (e.g. C2-C3alkynyl-CH(Me)-), C3-C6cycloalkyl or C1-
a4alkoxyC1-C4alkyl.
In a preferable embodiment, G is hydrogen, or an agriculturally acceptable
alkali metal or
alkaline earth metal, or an agriculturally acceptable sulfonium or ammonium
group. More
preferably, G is hydrogen, or an agriculturally acceptable alkali metal or
alkaline earth metal.
In a preferable embodiment, G is hydrogen, -C(X8)-R5 or -C(Xb)-Xc-Rb.
Most preferably G is hydrogen.
In one particular embodiment of the invention, X is chlorine.

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However, in the present invention, most preferably, X is methyl.
In one preferable embodiment of the invention, R1 is chlorine.
However, in the present invention, most preferably, R1 is methyl.
Therefore, e.g. in all aspects and/or embodiments of the invention, most
preferably, X is
methyl, and R1 is methyl.
In an alternative, also highly preferable, embodiment of the invention (which
e.g. can apply to
all aspects and/or embodiments of the invention), X is methyl, and R1 is
chlorine.
In another alternative preferable embodiment of the invention (which e.g. can
apply to all
aspects and/or embodiments of the invention), X is chlorine, and R1 is methyl.
In an alternative particular embodiment of the invention (which e.g. can apply
to all aspects
and/or embodiments of the invention), X is chlorine, and R1 is chlorine.
In the invention, R2 is hydrogen, methyl, ethyl, n-propyl, cyclopropyl, vinyl,
ethynyl, fluorine,
chlorine, bromine, C1-C3alkoxy (e.g. methoxy, ethoxy, n-propoxy or
isopropoxy),
C1-C2fluoroalkoxy (e.g. Cifluoroalkoxy such as difluoromethoxy or
trifluoromethoxy; or e.g.
CF3CH20-), C1-C2alkoxy-C1-C3alkoxy-, or C1fluoroalkoxy-C1-C3alkoxy-.
Preferably, when R2 is 01-C2alkoxy-01-C3alkoxy- or C1fluoroalkoxy-01-C3alkoxy-
, then R2 is
R2A0-CH(R2B)-CH(R2c)-0-;
wherein R2A is 01-C2alkyl (in particular methyl) or Cifluoroalkyl; and
R2B and R2C are independently hydrogen or methyl, provided that one or both of
R2B and R2
are hydrogen.
Preferably, R2A is methyl or Cifluoroalkyl, more preferably methyl.

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Preferably, both of R2B and R2C are hydrogen.
More preferably, when R2 is 01-C2alkoxy-01-C3alkoxy- or C1fluoroalkoxy-C1-
C3alkoxy- (in
particular when R2 is R2A0-CH(R2B)-CH(R2c)-0-), then R2 is Me0-CH2-CH2-0-.
Preferably, e.g. in all aspects and/or embodiments of the invention, R2 is
hydrogen, methyl,
ethyl, n-propyl, cyclopropyl, vinyl, ethynyl, fluorine, chlorine, bromine,
methoxy, ethoxy or
fluoromethoxy (i.e. Cifluoroalkoxy). Alternatively, preferably, R2 is Me0-CH2-
CH2-0-.
Preferably, e.g. in all aspects and/or embodiments of the invention, R2 is
methyl, ethyl, n-
propyl, cyclopropyl, vinyl, ethynyl, fluorine, chlorine, bromine, methoxy,
ethoxy or
fluoromethoxy (i.e. Cifluoroalkoxy). Alternatively, preferably, R2 is Me0-CH2-
CH2-0-.
Alternatively or additionally, preferably, e.g. in all aspects and/or
embodiments of the
invention, R2 is hydrogen, methyl, ethyl, ethynyl, chlorine, methoxy or
fluoromethoxy (i.e.
Cifluoroalkoxy, e.g. monofluoromethoxy, difluoromethoxy or trifluoromethoxy).
Alternatively,
preferably, R2 is ethoxy or Me0-CH2-CH2-0-.
More preferably, e.g. in all aspects and/or embodiments of the invention, R2
is not hydrogen.
More preferably, e.g. in all aspects and/or embodiments of the invention, R2
is methyl, ethyl,
ethynyl, chlorine, methoxy or fluoromethoxy (i.e. Cifluoroalkoxy, e.g.
monofluoromethoxy,
difluoromethoxy or trifluoromethoxy). Alternatively, more preferably, R2 is
ethoxy or
Me0-CH2-CH2-0-, preferably ethoxy.
Even more preferably, e.g. in all aspects and/or embodiments of the invention,
R2 is methyl,
ethynyl, chlorine or methoxy. Alternatively, even more preferably, R2 is
ethoxy.
Still more preferably, e.g. in all aspects and/or embodiments of the
invention, R2 is methyl,
chlorine or methoxy. Alternatively, still more preferably, R2 is ethoxy.
Yet more preferably, e.g. in all aspects and/or embodiments of the invention,
R2 is methyl or
methoxy.

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Most preferably, e.g. in all aspects and/or embodiments of the invention, R2
is methyl.
Therefore, more preferably, e.g. in all aspects and/or embodiments of the
invention:
R1 is methyl, and
R2 is methyl, ethyl, ethynyl, chlorine, methoxy or fluoromethoxy; still more
preferably methyl,
chlorine or methoxy; yet more preferably methyl or methoxy; most preferably
methyl.
In an alternative more preferable embodiment, e.g. in all aspects and/or
embodiments of the
invention:
R1 is chlorine, and
R2 is ethyl, ethynyl, chlorine, methoxy or fluoromethoxy; still more
preferably chlorine or
methoxy; most preferably methoxy.
In a further alternative more preferable embodiment, e.g. in all aspects
and/or embodiments
of the invention:
R1 is chlorine, and
R2 is ethoxy or Me0-CH2-CH2-0-, still more preferably ethoxy.
In a most preferable embodiment of the invention (which e.g. can apply to all
aspects and/or
embodiments of the invention), al is methyl, R2 is methyl, and X is methyl or
chlorine (most
preferably methyl).
In an alternative highly preferable embodiment of the invention (which e.g.
can apply to all
aspects and/or embodiments of the invention), al is methyl, R2 is chlorine,
and X is methyl or
chlorine (preferably methyl).
In an alternative preferable embodiment of the invention (which e.g. can apply
to all aspects
and/or embodiments of the invention), al is methyl, R2 is ethynyl, and X is
methyl or chlorine
(preferably methyl).

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In an alternative preferable embodiment of the invention (which e.g. can apply
to all aspects
and/or embodiments of the invention), R1 is methyl, R2 is methoxy, and X is
methyl or
chlorine (preferably methyl).
In an alternative particular embodiment of the invention (which e.g. can apply
to all aspects
and/or embodiments of the invention), R1 is methyl, R2 is hydrogen, and X is
methyl or
chlorine (preferably methyl).
In an alternative very highly preferable embodiment of the invention (which
e.g. can apply to
all aspects and/or embodiments of the invention), R1 is chlorine, R2 is
methoxy, and X is
methyl or chlorine (preferably methyl).
In an alternative highly preferable embodiment of the invention (which e.g.
can apply to all
aspects and/or embodiments of the invention), R1 is chlorine, R2 is chlorine,
and X is methyl
or chlorine (preferably methyl).
In an alternative particular embodiment of the invention (which e.g. can apply
to all aspects
and/or embodiments of the invention), R1 is chlorine, R2 is hydrogen, and X is
methyl or
chlorine (preferably methyl).
In an alternative highly preferable embodiment of the invention (which e.g.
can apply to all
aspects and/or embodiments of the invention), R1 is chlorine, R2 is ethoxy,
and X is methyl or
chlorine (preferably methyl).
Preferably, e.g. in all aspects and/or embodiments of the invention, when R4
and R5 are
taken together, then R4 and R5 taken together are -(CH2)n4- or -(CHA5-
C(R7a)(R7b)-(CHA6-=
Preferably, R7a is C1-C2alkyl; and R7b is hydrogen or C1-C2alkyl.
Preferably, n4 is 2 or 3.
Preferably, n5 and n6 are independently 0, 1 or 2 provided that n5 + n6 is 1
or 2.

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Preferably, e.g. in all aspects and/or embodiments of the invention, when R4
and R6 are
taken together (which is preferable), then R4 and R6 taken together
are -(CH2)54- or -(CH2)n5-C(R7a)(R7b)-(CH2)n6-;
wherein R7a is 01-C2alkyl; R7b is hydrogen or 01-C2alkyl;
n4 is 1, 2 or 3 (preferably 2 or 3); and
n5 and n6 are independently 0, 1 or 2 provided that n5 + n6 is 0, 1 or 2
(preferably 1 or 2).
Preferably, e.g. in all aspects and/or embodiments of the invention, R3, R4,
R6 and/or R6,
independently of each other, are hydrogen, Cratalkyl (e.g. C1-C2alkyl), C2-
a4alkynyl (in
particular 02-C3alkynyl-CH2-, e.g. ethynyl-CH2-), C1-C3alkoxyC1-C3alkyl, C1-
C3alkylthioC1-
C3alkyl, 01-C3alkylsulfinylC1-C3alkyl, 01-C3alkylsulfonylC1-C3alkyl; C3-
C4cycloalkyl (in
particular cyclopropyl); or an unsubstituted 4, 5 or 6 (e.g. 4 or 5) membered
monocyclic
heterocyclyl having one ring heteroatom independently selected from oxygen,
sulfur and
nitrogen, and attached at a ring carbon atom within the heterocyclyl (in
particular
tetrahydrofuranyl such as tetrahydrofuran-3-yl, or tetrahydropyranyl such as
tetrahydropyran-
provided that no more than one (in particular none) of R3, R4, R6 and R6 is
alkenyl, alkynyl,
alkoxyalkyl, alkylthioalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl,
cycloalkyl or heterocyclyl;
or R3 and R4 taken together are -(CH2)n1- or -(CH2)2-X1-(CH2)3- and R6 and R6
are as
defined herein (e.g. hereinabove), or R6 and R6 taken together
are -(CH2)51- or -(CH2)n2-X1-(CH2)3- and R3 and R4 are as defined herein (e.g.
hereinabove);
wherein X1 is 0, S, 3(0), S(0)2, NH, N(01-C2alkyl), N(01-C2alkoxy), C(H)(C1-
C2alkyl),
C(01-C2alky1)2 or C(H)(C1-C2alkoxy);
n1 is 4 or 5; and
n2 and n3 are independently 1, 2 or 3 provided that n2 + n3 is 3 or 4;
and/or R4 and R6 taken together are -(CH2)54- or -(CH2)n5-C(R70)(R7b)-(CH2)n6-
;
wherein R7a is C1-C2alkyl; R7b is hydrogen or C1-C2alkyl;
n4 is 1, 2 or 3 (in particular 2 or 3); and
n5 and n6 are independently 0, 1 or 2 provided that n5 + n6 is 0, 1 or 2 (in
particular 1 or 2).

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More preferably, e.g. in all aspects and/or embodiments of the invention, R3,
R4, R5 and/or
R6, independently of each other, are hydrogen, Cratalkyl (e.g. C1-C2alkyl), 02-
a4alkynyl (in
particular 02-C3alkynyl-CH2-, e.g. ethynyl-CH2-), 01-C3alkoxyC1-C3alkyl (in
particular
C1-C2alkoxyC1-C2alkyl), 01-C3alkylthioC1-C3alkyl (in particular 01-
C2alkylthioC1-C2alkyl),
C1-C3alkylsulfinylC1-C3alkyl (in particular Ci-C2alkylsulfinylCi-C2alkyl),
C1-C3alkylsulfonylC1-C3alkyl (in particular Ci-C2alkylsulfonylC1-C2alkyl); 03-
C4cycloalkyl (in
particular cyclopropyl); or an unsubstituted 4, 5 or 6 (e.g. 4 or 5) membered
monocyclic
heterocyclyl having one ring heteroatom independently selected from oxygen,
sulfur and
nitrogen, and attached at a ring carbon atom within the heterocyclyl (in
particular
tetrahydrofuranyl such as tetrahydrofuran-3-yl, or tetrahydropyranyl such as
tetrahydropyran-
4-yI);
provided that no more than one (in particular none) of R3, R4, R5 and R6 is
alkenyl, alkynyl,
alkoxyalkyl, alkylthioalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl,
cycloalkyl or heterocyclyl;
and/or R4 and R5 taken together are -(CI-12)n4- or -(CH2)n5-C(R7a)(R7b)-(CHA6-
;
wherein R78 is 01-C2alkyl; R7b is hydrogen or 01-C2alkyl;
n4 is 2 or 3; and
n5 and n6 are independently 0, 1 or 2 provided that n5 + n6 is 1 or 2.
Still more preferably, R3, R4, R5 and/or R6, independently of each other, are
hydrogen,
C1-C3alkyl (in particular 01-C2alkyl such as methyl) or 01-C3alkoxyC1-C3alkyl
(in particular
C1-C2alkoxyC1-C2alkyl); provided that no more than one (in particular none) of
R3, R4, R5 and
R6 is alkoxyalkyl;
and/or R4 and R5 taken together are -(CH2)4- or -(CHA5-C(R7a)(Rib)-(CHA6-;
wherein Ria is C1-C2alkyl; Rib is hydrogen or C1-C2alkyl;
n4 is 2 or 3; and
n5 and n6 are independently 0, 1 or 2 provided that n5 + n6 is 1 or 2.
Even more preferably, R3, R4, R5 and/or R6, independently of each other, are
hydrogen or C-
C2alkyl (preferably hydrogen or methyl); and/or R4 and R5 taken together
are -(CH2)54- wherein n4 is 2 or 3.

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Most preferably (especially when Y is CR8R9 or _0R10R11cR12R13_), R3, 4, 1-<¨
R5 and R6 are
hydrogen; or R4 and R5 taken together are -(CH2)54- wherein n4 is 2 or 3, and
R3 and R6 are
hydrogen.
.. Preferably, e.g. in all aspects and/or embodiments of the invention, at
least one (more
preferably 2, 3 or 4, still more preferably 3 or 4, most preferably all four)
of R3, R4, R5 and R6,
independently of each other, are hydrogen or 01-C4alkyl (e.g. H or 01-C3alkyl,
or H or
C1-C2alkyl);
or R4 and R5 are taken together as described herein.
Preferably, e.g. in all aspects and/or embodiments of the invention, Y is 0,
S, 3(0), S(0)2,
C(0), CR8R9or
More preferably, Y is 0, C(0), CR8R9or
Even more preferably, Y is 0 or CR8R9, in particular 0 or CH2.
Most preferably, Y is CR8R9, in particular CH2.
Preferably, e.g. in all aspects and/or embodiments of the invention, in R8 and
R9, one or both
of R8 and R9 is or are hydrogen; or R8 and R9 taken together are -(CH2)57- or
preferably
-(CH2)n8-X2-(CH2)n9-= In this embodiment, preferably Y is CR8R9 and/or
preferably X2 is 0.
In one particular embodiment, R8 and R9 are taken together and are -(CH2)õ7-
or preferably
-(CH2)58-X2-(CH2)59-= In this embodiment, preferably Y is CR8R9 and/or
preferably X2 is 0.
Preferably, e.g. in all aspects and/or embodiments of the invention, X2 is 0,
S, 3(0), 3(0)2,
.. C(H)(C1-C3alkyl), C(C1-C2alky1)2 or C(H)(C1-C3alkoxy). Most preferably, X2
is 0.
Preferably, n7 is 2, 3, 4 or 5, more preferably 4 or 5.
Preferably, n8 and n9 are independently 1, 2 or 3 provided that n8 + n9 is 2,
3 or 4.

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Preferably, n8 + n9 is 3 or 4. Most preferably, n8 is 2 and n9 is 2 (in which
case, preferably,
X2 is 0).
Preferably, e.g. in all aspects and/or embodiments of the invention, R8 and R9
are,
independently of each other:
hydrogen, Cratalkyl (in particular C1-C2alkyl), 02-C3alkenyl-CH2- (in
particular
ethenyl-0H2-), 02-C3alkynyl-0H2- (in particular ethynyl-0H2-), 01-
C2fluoroalkyl (in particular
Cifluoroalkyl), C1-C3alkoxyC1-C3alkyl, C1-C3alkylthioC1-C3alkyl,
or C1-C3alkylsulfonylC1-C3alkyl;
C3-C6cycloalkyl or C3-C6cycloalkyl substituted by one or two substituents
which
independently are C1-C3alkyl (in particular methyl or ethyl) or C1-
C2fluoroalkyl; and in which
one ring CH2 moiety of a 04-C6cycloalkyl is optionally (e.g. preferably)
replaced by an oxygen
or sulfur atom or by a S(0), S(0)2, NH, N(01-C3alkyl), N(01-C2fluoroalkyl),
N[C(0)01-C3alkyl],
N[C(0)C1-C2fluoroalkyl] or N(C1-C2alkoxy) moiety;
C3-C6cycloalkyl substituted by one substituent being 01-C3alkoxy (in
particular
C1-C2alkoxy) and optionally further substituted by one substituent being C1-
C2alkyl (in
particular methyl);
C3-C6cycloalkylC1-C2alkyl- (in particular 03-C6cycloalkylmethyl-) or 03-
C6cycloalkylC1-
C2alkyl- (in particular C3-C6cycloalkylmethyl-) substituted by one or two ring
substituents
which independently are C1-C3alkyl or C1-C2fluoroalkyl; and in which one ring
CH2 moiety of a
C4-C6cycloalkylC1-C2alkyl- (in particular 04-C6cycloalkylmethyl-) is
optionally (e.g. preferably)
replaced by an oxygen or sulfur atom or by a S(0), S(0)2, NH, N(C1-C2alkyl),
N(C1-
C2fluoroalkyl), N[C(0)01-C3alkyl], N[C(0)Ci-C2fluoroalkyl] or N(C1-C2alkoxy)
moiety;
C3-C6cycloalkylC1-C2alkyl- (in particular 03-C6cycloalkylmethyl-) substituted
by one ring
substituent being C1-C3alkoxy (in particular C1-C2alkoxy) and optionally
further substituted by
one ring substituent being 01-C2alkyl (in particular methyl); or
Het or Het-CH2-, wherein Het is a heteroaryl, attached at a ring-carbon, which
is
optionally substituted by 1,2 or 3 (in particular 1 or 2, e.g. 1) ring-carbon
substituents
independently being 01-C3alkyl (e.g. 01-C2alkyl), C1-C2fluoroalkyl, 01-C3alkyl-
C(0)-,
Ci-02f1u010a1ky1-C(0)-, hydroxy (including any oxo tautomer), 02-C3alkenyl
(e.g. ethenyl or
prop-1-enyl), C2-C3alkynyl (e.g. ethynyl or prop-1-ynyl), 01-C3alkoxy (e.g. Ci-
C2alkoxy),
C2fluoroalkoxy, halogen (e.g. fluorine or chlorine), cyano or nitro, provided
that any non-
fluorine halogen, alkoxy or fluoroalkoxy is not substituted at any ring-carbon
bonded directly
to a ring-nitrogen of the heteroaryl; and/or, in the case of a 5-membered
heteroaryl ring

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containing a ring-nitrogen atom not partaking in a C=N ring double bond, the
heteroaryl is
optionally substituted on the ring-nitrogen atom not partaking in a C=N ring
double bond by
one 01-C3alkyl, 01-C2fluoroalkyl, C1-03a1ky1-C(0)-, Ci-C2fluoroalkyl-C(0)- or
C1-C2alkyl-S(0)2- substituent;
provided that no more than one of R8 and R9 is an optionally substituted
cycloalkyl; an
optionally substituted cycloalkyl in which one ring CH2 moiety has been
replaced by an
oxygen or sulfur atom or by a S(0), S(0)2, NH, N(01-03a1ky1), N(C1-
C2fluoroalkyl),
N[C(0)01-03a1ky1], N[C(0)01-C2fluoroalkyl] or N(01-C2alkoxy) moiety; an
optionally
substituted cycloalkenyl; an optionally substituted cycloalkyl-alkyl-; an
optionally substituted
cycloalkyl-alkyl- in which one ring CH2 moiety has been replaced by an oxygen
or sulfur atom
or by a S(0), S(0)2, NH, N(01-C3alkyl), N(01-02f1u0r0a1ky1), N[C(0)C1-
C3alkyl],
N[C(0)01-C2fluoroalkyl] or N(C1-C2alkoxy) moiety; or Het or Het-CH2-;
or R8 is hydrogen or 01-C2alkyl (in particular H or Me), and R9 is 01-C2alkoxy
(in particular
methoxy);
or R8 and R9 taken together are -(CH2)7- or -(CHA8-X2-(CF12)0-.
In the above preferred embodiment, preferably Y is 0R8R9and/or preferably X2
is 0.
More preferably, e.g. in all aspects and/or embodiments of the invention:
R8 is hydrogen or C1-02a1ky1 (preferably H or Me, more preferably hydrogen);
and
R9 is:
01-02a1koxy (in particular methoxy);
02-03a1kyny1-0H2- (in particular ethynyl-0H2-);
01-C3alkoxyC1-03a1ky1;
01-03a1ky1thi001-C3alkyl (preferably 01-02a1ky1thio-0H20H2- or more preferably
Ci-02a1ky1thi0-CH(Me)0H2-);
01-C3alkylsulfinylC1-03a1ky1;
01-C3alkylsulfonylC1-03a1ky1;
03-C6cycloalkyl or 03-C6cycloalkyl substituted by one or two substituents
which
independently are C1-03a1ky1 (in particular methyl or ethyl) or 01-
C2fluoroalkyl; and in which
one ring CH2 moiety of a 04-06cyc10a1ky1 is optionally (e.g. preferably)
replaced by an oxygen

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or sulfur atom or by a S(0), S(0)2, NH, N(01-C3alkyl), N(01-C2fluoroalkyl),
N[C(0)01-C3alkyl],
N[C(0)C1-C2fluoroalkyl] or N(01-C2alkoxy) moiety (or more preferably is
replaced by an
oxygen or sulfur atom or by a S(0), S(0)2, NH, N(Ci-C3alkyl) or N(01-C2alkoxy)
moiety; or
still more preferably is replaced by an oxygen or sulfur atom);
C3-C6cycloalkyl substituted by one substituent being C1-C3alkoxy (in
particular
Ci-C2alkoxy) and optionally further substituted by one substituent being C1-
C2alkyl (in
particular methyl);
C3-C6cycloalkylmethyl- or C3-C6cycloalkylmethyl- substituted by one or two
ring
substituents which independently are 01-C3alkyl (in particular C1-C2alkyl) or
01-C2fluoroalkyl;
and in which one ring CH2 moiety of a 04-C6cycloalkylmethyl- is optionally
(e.g. preferably)
replaced by an oxygen or sulfur atom or by a S(0), S(0)2, NH, N(C1-C2alkyl),
N(C1-
C2fluoroalkyl), N[C(0)01-C3alkyl], N[C(0)Ci-C2fluoroalkyl] or N(C1-C2alkoxy)
moiety (or more
preferably is replaced by an oxygen or sulfur atom or by a N[C(0)01-C3alkyl]
or
N[C(0)Ci-C2fluoroalkyl] moiety);
C3-C6cycloalkylmethyl- substituted by one ring substituent being C1-C3alkoxy
(in
particular 01-C2alkoxy) and optionally further substituted by one ring
substituent being
C1-C2alkyl (in particular methyl); or
Het or Het-CH2-, wherein Het is a heteroaryl, attached at a ring-carbon, which
is
optionally substituted by 1,2 or 3 (in particular 1 or 2, e.g. 1) ring-carbon
substituents
independently being 01-C3alkyl (in particular C1-C2alkyl), C1-C2fluoroalkyl
(in particular
Cifluoroalkyl), 01-C3alkyl-C(0)-, 01-C2fluoroalkyl-C(0)-, hydroxy (including
any oxo
tautomer), C2-C3alkenyl (in particular ethenyl or prop-1-enyl), C2-C3alkynyl
(in particular
ethynyl or prop-1-ynyl), C1-C3alkoxy (in particular 01-C2alkoxy), C1-
C2fluoroalkoxy (in
particular Cifluoroalkoxy), halogen (in particular fluorine or chlorine),
cyano or nitro, provided
that any non-fluorine halogen, alkoxy or fluoroalkoxy is not substituted at
any ring-carbon
bonded directly to a ring-nitrogen of the heteroaryl; and/or, in the case of a
5-membered
heteroaryl ring containing a ring-nitrogen atom not partaking in a C=N ring
double bond, the
heteroaryl is optionally substituted on the ring-nitrogen atom not partaking
in a C=N ring
double bond by one 01-C3alkyl, 01-C2fluoroalkyl, C1-C3alkyl-C(0)-, C1-
C2fluoroalkyl-C(0)- or
C1-C2alkyl-S(0)2- substituent;
or R8 and R9 taken together are -(CH2)7- or -(CH2)8-X2-(C1-12)n9-=
In the above more preferred embodiment, preferably Y is CR8R9 and/or
preferably X2 is 0.

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Even more preferably, e.g. in all aspects and/or embodiments of the invention:
R8 is hydrogen or 01-02a1ky1 (preferably H or Me, more preferably hydrogen);
and
R9 is:
01-C3alkylthioC1-C3alkyl (preferably 01-C2alkylthio-CH2CH2- or more preferably
C1-C2alkylthio-CH(Me)0H2-);
C3-C6cycloalkyl or C3-C6cycloalkyl substituted by one or two substituents
which
independently are C1-C3alkyl (in particular methyl or ethyl) or 01-
C2fluoroalkyl; and in which
.. one ring CH2 moiety of a 04-06cyc10a1ky1 is replaced by an oxygen or sulfur
atom or by a
S(0), S(0)2, NH, N(C1-C3alkyl), N(01-C2fluoroalkyl), N[C(0)C1-C3alkyl],
N[C(0)01-C2fluoroalkyl] or N(01-C2alkoxy) moiety (or preferably is replaced by
an oxygen or
sulfur atom or by a S(0), 3(0)2, NH, N(01-C3alkyl) or N(C1-02a1k0xy) moiety;
or more
preferably is replaced by an oxygen or sulfur atom);
C3-06cyc10a1ky1methy1- or 03-C6cycloalkylmethyl- substituted by one or two
ring
substituents which independently are 01-03a1ky1 (in particular C1-C2alkyl) or
01-02f1u0r0a1ky1;
and in which one ring CH2 moiety of a 04-C6cycloalkylmethyl- is replaced by an
oxygen or
sulfur atom or by a S(0), 3(0)2, NH, N(01-C2alkyl), N(01-C2fluoroalkyl),
N[C(0)01-C3alkyl],
N[C(0)C1-C2fluoroalkyl] or N(Ci-C2alkoxy) moiety (or preferably is replaced by
an oxygen or
sulfur atom or by a N[C(0)01-C3alkyl] or N[C(0)01-C2fluoroalkyl] moiety); or
Het or Het-CH2-, wherein Het is a heteroaryl, attached at a ring-carbon, which
is
optionally substituted by 1,2 or 3 (in particular 1 or 2, e.g. 1) ring-carbon
substituents
independently being 01-C3alkyl (in particular C1-C2alkyl), 01-C2fluoroalkyl
(in particular
Cifluoroalkyl), 01-C3alkyl-C(0)-, 01-02f1u0r0a1ky1-C(0)-, hydroxy (including
any oxo
tautomer), 02-C3alkenyl (in particular ethenyl or prop-1-enyl), 02-C3alkynyl
(in particular
ethynyl or prop-1-ynyl), 01-C3alkoxy (in particular 01-C2alkoxy), 01-
C2fluoroalkoxy (in
particular Cifluoroalkoxy), halogen (in particular fluorine or chlorine),
cyano or nitro, provided
that any non-fluorine halogen, alkoxy or fluoroalkoxy is not substituted at
any ring-carbon
bonded directly to a ring-nitrogen of the heteroaryl; and/or, in the case of a
5-membered
heteroaryl ring containing a ring-nitrogen atom not partaking in a C=N ring
double bond, the
heteroaryl is optionally substituted on the ring-nitrogen atom not partaking
in a C=N ring
double bond by one 01-C3alkyl, 01-C2fluoroalkyl, C1-C3alkyl-C(0)-, C1-
C2fluoroalkyl-C(0)- or
Ci-02a1ky1-S(0)2- substituent;

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or R8 and R9 taken together are -(CH2)7- or -(C1-12)ns-X2-(C1-12)n9-=
In the above even more preferred embodiment, preferably Y is CR8R9 and/or
preferably X2 is
0.
In one preferable embodiment (which e.g. can apply to all aspects and/or
embodiments of
the invention), R8 and R9 are, independently of each other, hydrogen or C1-
C3alkyl
(preferably hydrogen or C1-C2alkyl, such as hydrogen or methyl). In this
embodiment,
preferably, Y is CR8R9.
In another preferable embodiment (which e.g. can apply to all aspects and/or
embodiments
of the invention), R8 is hydrogen, and R9 is C1-C3alkylthioC1-C3alkyl. In this
embodiment, R9
preferably is 01-C2alkylthio-CH2CH2- or more preferably is C1-C2alkylthio-
CH(Me)CH2-. In
this embodiment, preferably, Y is CR8R9.
In another preferable embodiment (which e.g. can apply to all aspects and/or
embodiments
of the invention), R8 is hydrogen and R9 is 04-C6cycloalkylmethyl- or
C4-C6cycloalkylmethyl- substituted by one or two ring substituents which
independently are
Ci-C3alkyl (in particular Ci-C2alkyl) or C1-C2fluoroalkyl, and in which one
ring CH2 moiety is
replaced by an oxygen or sulfur atom or by a S(0), S(0)2, NH, N(C1-C2alkyl),
N(C1-
C2fluoroalkyl), N[C(0)C1-C3alkyl], N[C(0)01-C2fluoroalkyl] or N(01-C2alkoxy)
moiety (or more
preferably is replaced by an oxygen or sulfur atom or by a N[C(0)C1-C3alkyl]
or
N[C(0)C1-C2fluoroalkyl] moiety). In this embodiment, preferably, Y is CR8R9.
In this preferable embodiment, then more preferably R8 is hydrogen and R9 is a
heterocyclyl-methyl-, wherein the heterocyclyl is Q, wherein Q is one of the
following sub-
formulae Q1, 02, 03, 04, 05, Q65 079 Q339 0349 0379 0389 0419 0423 0439 0445
0479 0875 0899 090 or
0107
Cr-A
\-0 0
QA
Q1 Q2 Q3 Q4 Q5

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r-' --
a s' 0.--A S
A 1%.'''.ik S...,õ,.--..õ
A A
0/1
037
Q6 Q, 033 034
O=S A Sr.-- l'.
0 =S...,,,,^\, 0 ===,.
S 0
0 =S
i I .......,\,..
1 I (Y A II A L'=-A L..-
0 0
Q38 Q41 Q42 Q43 044
0 I
R(N-A ,s9A n,9A r-' 1-<
,-N, ./'==
N n \
N
A
9A/ ___________________ r
N
R9AN ...,.....õ..---..,
A '..sA I __
A
Q47 Q87
Q89
Q90 Q107
wherein:
A is the position of attachment to the -methyl- moiety; and
R9A is hydrogen, C1-C2alkyl (e.g. methyl), 01-C2fluoroalkyl (e.g.
Cifluoroalkyl), -C(0)C1-C3alkyl (e.g. -C(0)methyl), -C(0)C1-C2fluoroalkyl
(e.g. -C(0)Cifluoroalkyl) or C1-C2alkoxy.
More preferably, Q is one of the sub-formulae 01, 02, 04, 069 079 0339 0349
0419 042, 043, 0449
¨2, ¨6, ¨7, ¨33, ¨34, ¨41,
087, Q89 or Q90. Even more preferably, Q is one of the sub-formulae 0 10 0 01
0 0
0429 0439 0449 0879 Q89 or 090.
Yet more preferably, Q is one of the sub-formulae Q2, Q7, Q87 or Q90. Further
more
preferably, Q is one of the sub-formulae 02, 07 or 090.
Most preferably, Q is sub-formula Q7.
Preferably, R9A is -C(0)C1-C3alkyl (e.g. -C(0)methyl) or -C(0)01-C2fluoroalkyl
(e.g. -C(0)C1fluoroalkyl).
In one preferable embodiment of the invention (which e.g. can apply to all
aspects and/or
embodiments of the invention), R8 is hydrogen, and R9 is tetrahydro-2H-pyran-4-
y1(

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) or (tetrahydro-2H-pyran-4-yI)-methyl-. In this embodiment, preferably, Y is
CR8R9. When R9 is (tetrahydro-2H-pyran-4-yI)-methyl-, then R9 is Q7-methyl-
wherein Q7 is
wherein A is the position of attachment to the -methyl- moiety.
In another preferable embodiment (which e.g. can apply to all aspects and/or
embodiments
of the invention), R8 is hydrogen and R9 is Het or Het-CH2- as defined herein.
In this
embodiment, more preferably, R8 is hydrogen and R9 is Het as defined herein.
In this
embodiment, preferably, Y is CR8R9.
Preferably, e.g. in all aspects and/or embodiments of the invention, Het is a
heteroaryl (in
particular monocyclic heteroaryl), attached at a ring-carbon, which is
optionally substituted by
1,2 or 3 (in particular 1 or 2, e.g. 1) ring-carbon substituents independently
being C1-C2alkyl,
Cifluoroalkyl, 01-C2alkyl-C(0)-, C1fluoroalkyl-C(0)-, hydroxy (including any
oxo tautomer),
ethynyl, prop-1-ynyl, C1-C2alkoxy, Cifluoroalkoxy, fluorine, chlorine,
bromine, cyano or nitro,
provided that any chlorine, bromine, alkoxy or fluoroalkoxy is not substituted
at any
ring-carbon bonded directly to a ring-nitrogen of the heteroaryl;
and/or, in the case of a 5-membered heteroaryl ring containing a ring-nitrogen
atom not
partaking in a C=N ring double bond, the heteroaryl is optionally substituted
on the ring-
nitrogen atom not partaking in a C=N ring double bond by one C1-C3alkyl, 01-
C2fluoroalkyl,
Ci-C3alkyl-C(0)-, C1-C2fluoroalkyl-C(0)- or C1-C2alkyl-S(0)2- substituent.
More preferably, e.g. in all aspects and/or embodiments of the invention, Het
is a heteroaryl
(in particular monocyclic heteroaryl), attached at a ring-carbon, which is
optionally substituted
by 1 or 2 (in particular 1) ring-carbon substituents independently being C1-
C2alkyl (in
particular methyl), Cifluoroalkyl (in particular CF3), C1-C2alkyl-C(0)- (in
particular Me-C(0)-),
C1fluoroalkyl-C(0)-, ethynyl, prop-l-ynyl, fluorine or cyano;
and/or, in the case of a 5-membered heteroaryl ring containing a ring-nitrogen
atom not
partaking in a C=N ring double bond, the heteroaryl is optionally substituted
on the ring-

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nitrogen atom not partaking in a C=N ring double bond by one C1-C2alkyl (e.g.
methyl),
Cifluoroalkyl, methyl-C(0)- or Cifluoroalkyl-C(0)- substituent.
More preferably, e.g. in all aspects and/or embodiments of the invention, Het
is a heteroaryl
(in particular monocyclic heteroaryl), attached at a ring-carbon, which is
optionally substituted
by 1 or 2 (in particular 1) ring-carbon substituents independently being 01-
C2alkyl (in
particular methyl), Cifluoroalkyl (in particular CF3), fluorine or cyano;
and/or, in the case of a 5-membered heteroaryl ring containing a ring-nitrogen
atom not
partaking in a C=N ring double bond, the heteroaryl is optionally substituted
on the ring-
nitrogen atom not partaking in a C=N ring double bond by one methyl
substituent.
Preferably, e.g. in all aspects and/or embodiments of the invention, Het is an
optionally
substituted monocyclic heteroaryl, attached at a ring-carbon. Such as
monocyclic heteroaryl
can be 5-membered or 6-membered monocyclic heteroaryl.
More preferably, e.g. in all aspects and/or embodiments of the invention, Het
is an optionally
substituted monocyclic heteroaryl, attached at a ring-carbon, which is:
pyridinyl (preferably pyridin-3-y1 or most preferably pyridin-2-y1), pyrazolyl
(preferably pyrazol-
5-y1 or pyrazol-4-yl, or most preferably pyrazol-3-y1), imidazolyl (preferably
imidazol-2-y1),
pyrazinyl, pyrimidinyl (preferably pyrimidin-4-y1), pyridazinyl (preferably
pyridazin-3-y1),
triazolyl (e.g. 1,2,3-triazoly1), tetrazol-5-yl, oxazolyl, thiazolyl,
isoxazolyl, isothiazolyl or
oxadiazolyl; optionally present (e.g. where chemically possible) as an
agrochemically
acceptable salt thereof (such as an agrochemically acceptable acid addition
salt thereof).
Even more preferably, e.g. in all aspects and/or embodiments of the invention,
Het is an
optionally substituted monocyclic heteroaryl, attached at a ring-carbon, which
is:
pyridinyl (preferably pyridin-3-y1 or most preferably pyridin-2-y1), pyrazolyl
(preferably pyrazol-
5-y1 or pyrazol-4-yl, or most preferably pyrazol-3-y1), imidazolyl (preferably
imidazol-2-y1),
pyrazinyl, pyrimidinyl (preferably pyrimidin-4-y1), pyridazinyl (preferably
pyridazin-3-y1),
triazolyl (e.g. 1,2,3-triazoly1), or tetrazol-5-y1; optionally present (e.g.
where chemically
possible) as an agrochemically acceptable salt thereof (such as an
agrochemically
acceptable acid addition salt thereof).

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Still more preferably, e.g. in all aspects and/or embodiments of the
invention, Het is an
optionally substituted monocyclic heteroaryl, attached at a ring-carbon, which
is:
pyridinyl (preferably pyridin-3-y1 or most preferably pyridin-2-y1), pyrazolyl
(preferably pyrazol-
5-y1 or pyrazol-4-yl, or most preferably pyrazol-3-y1), imidazolyl (preferably
imidazol-2-y1),
pyrazinyl, pyrimidinyl (preferably pyrimidin-4-y1), or pyridazinyl (preferably
pyridazin-3-y1);
optionally present (e.g. where chemically possible) as an agrochemically
acceptable salt
thereof (such as an agrochemically acceptable acid addition salt thereof).
Yet more preferably, e.g. in all aspects and/or embodiments of the invention,
Het is an
optionally substituted monocyclic heteroaryl, attached at a ring-carbon, which
is:
pyridin-3-yl, pyridin-2-yl, or pyrazolyl (preferably pyrazol-5-y1 or pyrazol-4-
yl, or most
preferably pyrazol-3-y1); optionally present (e.g. where chemically possible)
as an
agrochemically acceptable salt thereof (such as an agrochemically acceptable
acid addition
salt thereof).
Most preferably, e.g. in all aspects and/or embodiments of the invention, Het
is an optionally
substituted monocyclic heteroaryl, attached at a ring-carbon, which is:
pyridin-2-y1 or pyrazol-
3-y1; optionally present (e.g. where chemically possible) as an agrochemically
acceptable salt
thereof (such as an agrochemically acceptable acid addition salt thereof).
It is particularly preferred (e.g. in all aspects and/or embodiments of the
invention) that, in
Het, any ring-carbon atom, which is directly bonded to the ring-carbon atom
which is the
point of attachment (e.g. or i.e. which is the point of attachment to the
central carbon atom
within the Y = CR8R9 moiety (for Het), or which is the point of attachment to
the -CH2- moiety
(for Het-CH2-), is unsubstituted. Therefore, for example, preferably, when Het
is an
optionally substituted pyridin-2-y1 (optionally present as an agrochemically
acceptable salt
thereof), then the ring-carbon atom at the 3-position of the ring (calculated
with respect to the
pyridine ring nitrogen atom) is unsubstituted.
Preferably, e.g. in all aspects and/or embodiments of the invention, R10, R11,
R12 and/or R13
are, independently of each other, hydrogen or C1-C2alkyl (in particular
hydrogen or methyl).

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Preferably, two, three or all of R19, R11, R12 and K-13
are hydrogen.
Most preferably, R19, R11, R12 and K.--µ13
are hydrogen.
In a particularly preferable embodiment of the invention (which e.g. can apply
to all aspects
and/or embodiments of the invention):
Y is 0 or CR8R9 (preferably CR8R9); and
R4 and R6 are taken together and are -(CH2)n4- or -(CH2)n5-C(R7a)(R7b)-
(CH2),16-;
wherein R7a is 01-C2alkyl; R7b is hydrogen or 01-C2alkyl;
n4 is 2 or 3; and
n5 and n6 are independently 0, 1 or 2 provided that n5 + n6 is 1 or 2.
In this particularly preferable embodiment, more preferably, Y is 0 or CR8R9
(preferably
CR8R9) wherein R8 and R9 are, independently of each other, hydrogen or C1-
C3alkyl (in
particular, this 01-C3alkyl can be C1-C2alkyl such as methyl).
In this particularly preferable embodiment, even more preferably Y is 0 or CH2
; or, most
preferably, Y is CH2.
In this particularly preferable embodiment, more preferably, R3 and R6,
independently of each
other, are hydrogen, C1-C3alkyl (in particular C1-C2alkyl such as methyl) or
C1-C3alkoxyC1-C3alkyl (in particular C1-C2alkoxyC1-C2alkyl); provided that no
more than one
(in particular none) of R3 and R6 is alkoxyalkyl.
In this particularly preferable embodiment, even more preferably, R3 and R6,
independently of
each other, are hydrogen or 01-C2alkyl (preferably hydrogen or methyl); and R4
and R6 taken
together are -(CH2)n4- wherein n4 is 2 or 3.
In a particularly preferable embodiment of the invention (which e.g. can apply
to all aspects
and/or embodiments of the invention), the compound of formula (I) is a
compound described
in any of Tables 1 to 25, as described and/or illustrated herein, optionally
present (e.g. where
chemically possible) as an agrochemically acceptable salt thereof. In an
alternative

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particularly preferable embodiment of the invention (which e.g. can apply to
all aspects
and/or embodiments of the invention), the compound of formula (I) is a
compound described
Table 26 or 27, as described and/or illustrated herein, optionally present
(e.g. where
chemically possible) as an agrochemically acceptable salt thereof. More
preferably (e.g. in
all aspects and/or embodiments of the invention), the compound of formula (I)
is a compound
described in any of Tables 1, 3, 5, 8, 9, 10, 11, 12,14, 15,16, 17, 18, 19,
20, 21, 22, 23, 24
or 25 (or alternatively in Table 26 or 27), as described and/or illustrated
herein, optionally
present (e.g. where chemically possible) as an agrochemically acceptable salt
thereof. Even
more preferably (e.g. in all aspects and/or embodiments of the invention), the
compound of
formula (I) is a compound described in any of Tables 1, 3, 5, 8, 9, 10, 11,
12, 14, 15, 16 or 25
(or alternatively in Table 26 or 27), as described and/or illustrated herein,
optionally present
(e.g. where chemically possible) as an agrochemically acceptable salt thereof.
In one more particularly preferable embodiment of the invention (which e.g.
can apply to all
aspects and/or embodiments of the invention), the compound of formula (I) is
compound A-1,
A-2, A-3, A-4, A-5, A-6, A-7, A-8, A-9, A-10, A-11, A-12, A-13, A-14 or A-15,
as described
and/or illustrated herein, optionally present (e.g. where chemically possible)
as an
agrochemically acceptable salt thereof. In an alternative more particularly
preferable
embodiment of the invention (which e.g. can apply to all aspects and/or
embodiments of the
invention), the compound of formula (I) is compound A-16, A-17 or A-18, as
described and/or
illustrated herein, optionally present (e.g. where chemically possible) as an
agrochemically
acceptable salt thereof. In a further alternative more particularly preferable
embodiment of
the invention (which e.g. can apply to all aspects and/or embodiments of the
invention), the
compound of formula (I) is compound A-20 (= compound 11.10), A-22 (= compound
1.10),
A-25 (= compound 14.23), A-27 (= compound 12.02), A-28 (= compound 12.10), A-
30 (=
compound 12.15), A-31 (= compound 9.02), A-32 (= compound 9.10), A-33 (=
compound
1.02), A-34 (= compound 1.15), A-35 (= compound 5.02), A-36 (= compound 5.10),
A-37 (=
compound 5.15), A-38 (= compound 11.02), A-39 (= compound 11.15), A-40 (=
compound
25.10) or A-41 (= compound 14.06), as described and/or illustrated herein,
optionally present
(e.g. where chemically possible) as an agrochemically acceptable salt thereof.
In a further
alternative more particularly preferable embodiment of the invention (which
e.g. can apply to
all aspects and/or embodiments of the invention), the compound of formula (I)
is compound
A-19, A-21, A-23, A-24, A-26, A-29, P-3, P-4, P-5 or P-7, as described and/or
illustrated

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herein, optionally present (e.g. where chemically possible) as an
agrochemically acceptable
salt thereof.
In a yet more particularly preferable embodiment of the invention (which e.g.
can apply to all
aspects and/or embodiments of the invention), the compound of formula (I) is
compound A-2,
A-3, A-4, A-5, A-8, A-9, A-10, A-12, A-13, A-14, A-15, A-16, A-17 or A-18, as
described
and/or illustrated herein, optionally present (e.g. where chemically possible)
as an
agrochemically acceptable salt thereof; or alternatively is compound A-6, as
described and/or
illustrated herein, optionally present as an agrochemically acceptable salt
thereof. In an
alternative yet more particularly preferable embodiment of the invention
(which e.g. can apply
to all aspects and/or embodiments of the invention), the compound of formula
(I) is
compound A-20, A-22, A-27, A-28, A-33, A-34, A-35, A-36, A-38, A-39, A-40 or A-
41, as
described and/or illustrated herein, optionally present (e.g. where chemically
possible) as an
agrochemically acceptable salt thereof. In a further alternative yet more
particularly
preferable embodiment of the invention (which e.g. can apply to all aspects
and/or
embodiments of the invention), the compound of formula (I) is compound A-19, A-
21, A-23,
A-24, A-26, P-3, P-5 or P-7, as described and/or illustrated herein,
optionally present (e.g.
where chemically possible) as an agrochemically acceptable salt thereof.
Depending on the nature of the substituents G, R1, R2, R3, R4, R6, R6, R7 and
R8, compounds
of formula (I) may exist in different isomeric forms. When G is hydrogen, for
example,
compounds of formula (I) may exist in different tautomeric forms:
H, R
Ri
3 0 3 OR
0
R4 R4 R4
R2 R2 R2
0 0
5 R6 R5 R6 R5 R6 HI
Also, when substituents contain double bonds, cis- and trans-isomers can
exist. This
invention covers all such isomers and tautomers and mixtures thereof in all
proportions.
These isomers, too, are within the scope of the claimed compounds of the
formula (I).

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According to a further aspect of the invention, there is provided a compound
of formula
(ZZ):
XX
A
G CI
0
R4A
0
0
R9A
R5A (ZZ),
wherein:
XX is hydrogen or ethyl; and
R8A is hydrogen, and R9A is hydrogen, methyl, Ci-C2alkylthio-CH2CH2-,
C1-C2alkylthio-CH(Me)CH2-, tetrahydro-2H-pyran-4-yl, (tetrahydro-2H-pyran-4-
y1)-methyl-, or
pyridin-2-y1;
or R8A and R9A are methyl;
or R8A and R9A taken together are -CH2CH2-0-CH2CH2-; and
R4A and R5A are hydrogen; or R4A and R5A taken together are -CH2-CH2-;
provided that when R4A and R5A taken together are -CH2-CH2- then R8A and R9A
are
hydrogen; and
GA is hydrogen, an agriculturally acceptable metal, or an agriculturally
acceptable sulfonium
or ammonium group; or G is -C(0)-Ral or
wherein Ral is C1-C6alkyl, C2-C4alkenyl, C2-C4alkynyl, C3-C6cycloalkyl,
C3-C6cycloalkyl-methyl-, C1-C4alkoxyC1-C4alkyl, or phenyl or phenyl
substituted by 1, 2 or 3
of, independently, methyl, Cifluoroalkyl, methoxy, Cifluoroalkoxy, halogen,
cyano or nitro;
and Rbl is C1-C6alkyl, C2-C3alkenyl-CH2-, C2-C3alkenyl-CH(Me)-, 02-C3alkynyl-
CH2-,
C2-C3alkynyl-CH(Me)-, 03-C6cycloalkyl, C3-C6cycloalkyl-methyl-, 01-C4alkoxyC1-
a4alkyl, or
phenyl or phenyl substituted by 1, 2 or 3 of, independently, methyl,
Cifluoroalkyl, methoxy,
Cifluoroalkoxy, halogen, cyano or nitro;

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and wherein the compound of formula (ZZ) is optionally present (e.g. where
chemically
possible) as an agrochemically acceptable salt thereof.
Preferably, R8A is hydrogen, and R9A is hydrogen, C1-C2alkylthio-CH(Me)CH2-,
(tetrahydro-
2H-pyran-4-yI)-methyl-, or pyridin-2-y1;
or R8A and R9A are methyl;
or R8A and R9A taken together are -CH2CH2-0-CH2CH2-.
More preferably, RBA is hydrogen, and R9A is hydrogen, 01-C2alkylthio-
CH(Me)CH2-, or
pyridin-2-y1;
or R8A and R9A are methyl;
or R8A and R9A taken together are -CH2CH2-0-CH2CH2-.
Most preferably, R8A and R9A are hydrogen; or R8A and R9A taken together
are -CH2CH2-0-CH2CH2-.
Preferably, Ral is C1-C6alkyl. Preferably, Rbl is 01-C6alkyl.
Preferably, GA is hydrogen, an agriculturally acceptable metal, or an
agriculturally acceptable
sulfonium or ammonium group. Most preferably, GA is hydrogen.
In one particular embodiment, XX is hydrogen. In an alternative particular
embodiment, XX
is ethyl.
0CI
0
0
0
Preferably, the compound of formula (ZZ) is (B-1),

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CI CI
0 0
0 0
0 0
(B-2), (B-3), or
/7-
CI
0
0
0
(B-4),
optionally present as an agrochemically acceptable salt thereof.
According to a further aspect of the invention, there is provided a method of
controlling weeds
in crops of useful plants, comprising applying a compound of formula (ZZ), as
defined herein,
or a herbicidal composition comprising such a compound, to the plants or to
the locus
thereof. Preferably, the weeds comprise grassy monocotyledonous weeds. More
preferably,
the grassy monocotyledonous weeds comprise "warm season" (warm climate) grassy
monocotyledonous weeds, even more preferably weeds from the genus Brachiaria,
Cenchrus, Digitaria, Echinochloa, Eleusine, Eriochloa, Leptochloa, Ottochloa,
Panicum,
Pennisetum, Phalaris, Rottboellia, Setaria and/or Sorghum. Preferably, the
crops of useful
plants comprise wheat, barley, rye, triticale, sugarcane, soybean, peanut,
pulse crops, cotton,
rape, sunflower, linseed, sugarbeet, fodder beet, potato, and/or
dicotyledonous vegetables.
Typically, the rate of application (typically to the weeds and/or to the crops
of useful plants
and/or to the locus thereof) of the compound of formula (ZZ) (which optionally
may be an
agrochemically acceptable salt thereof) will be from 1 to 2000 g, in
particular from 5 to 1000
g/ha or from 10 to 1000 g/ha or from 10 to 500 g/ha, of the compound of
formula (ZZ)
(measured as the salt-free compound, i.e. excluding the weight of any
associated salt
counterion(s)). The compound of formula (ZZ) can be applied (typically to the
weeds and/or
to the crops of useful plants and/or to the locus thereof) pre- and/or post-
emergence, but
preferably is applied post-emergence.

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Processes for preparation of compounds, e.g. compounds of formula (I)
Processes for preparation of compounds, e.g. a compound of formula (I) (which
optionally
can be an agrochemically acceptable salt thereof), are now described, and form
further
aspects of the present invention.
A compound of formula I, wherein G is:
-C(X0)-Re, -C(Xb)-Xc-Rb, -C(Xd)-N(Rc)-Rd, -S02-Re, -P(Xe)(Rf)-Rg, -CH2-Xf-Rh;
or
.. phenyl-CH2- or phenyl-CH(C1-C2alkyl)- (in each of which the phenyl is
optionally substituted
by 1, 2 or 3 of, independently, C1-C2alkyl, Cifluoroalkyl, Ci-C2alkoxy,
Cifluoroalkoxy, fluorine,
chlorine, bromine, cyano or nitro), or heteroaryl-CH2- or heteroaryl-CH(01-
C2alkyl)- (in each
of which the heteroaryl is optionally substituted by 1, 2 or 3 of,
independently, 01-C2alkyl,
Cifluoroalkyl, C1-C2alkoxy, Cifluoroalkoxy, fluorine, chlorine, bromine, cyano
or nitro), or
phenyl-C(0)-CH2- (wherein the phenyl is optionally substituted by 1, 2 or 3
of, independently,
C1-C2alkyl, Cifluoroalkyl, Ci-C2alkoxy, Cifluoroalkoxy, fluorine, chlorine,
bromine, cyano or
nitro); or Ci-C6alkoxy-C(0)-CH2-, C1-C6alkoxy-C(0)-CH=CH-, 02-C7alken-1-yl-CH2-
,
C2-C7alken-1-yl-CH(Ci-C2alkyl)-, C2-C4fluoroalken-1-yl-CH2-, C2-C7alkyn-1-yl-
CH2-, or
C2-C7alkyn-1-yl-CH(C1-C2alkyl)-;
may be prepared by treating a compound of formula (A), which is a compound of
formula I
wherein G is H,
(a) with a reagent G1-Z, wherein G1-Z is an alkylating agent (wherein G1 is an
organic group
according to G within the compound of formula (I) and which is linked by a non-
carbonyl,
non-thiocarbonyl carbon atom) such as an organic halide (in which Z = halogen
such as
chlorine, bromine or iodine); wherein the organic halide (e.g. chloride) can
typically be a
substituted alkyl halide (e.g. chloride) such as a chloromethyl alkyl ether
CI¨CH2-Xf-Rh
wherein Xf is oxygen, a chloromethyl alkyl sulfide CI¨CH2-Xf-R" wherein Xf is
sulphur, a
suitable optionally substituted benzyl halide (e.g. chloride) such as CI-CH2-
[optionally
substituted phenyl], [optionally substituted phenyl]C(0)-CH2-[halogen e.g.
Cl],
C1-C6alkoxy-C(0)-CH2-[halogen e.g. CI], 01-C6alkoxy-C(0)-CH=CH-[halogen e.g.
Cl], a
suitable alkenyl or alkynyl halide (e.g. chloride) such as C2-C7alken-1-yl-CH2-
[halogen e.g.
Cl] or C2-C7alkyn-1-yl-CH2-[halogen e.g. Cl], or another organic halide
suitable for preparing
a (non-carbonyl, non-thiocarbonyl carbon)-linked G (or G1) group; or

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(b) [e.g. to prepare carbonyl-carbon-linked or thiocarbonyl-carbon-linked G
groups] with an
acylating agent such as a carboxylic acid, HO-C(Xa)Ra, wherein Xa is oxygen,
an acid
chloride, CI-C(Xa)Ra, wherein Xa is oxygen, or an acid anhydride, [RaC(V)]20,
wherein Xa is
oxygen, or an isocyanate, RcN=C=0, or a carbamoyl chloride, CI-C(Xd)-N(Rc)-Rd
(wherein Xd
is oxygen and with the proviso that neither IR or Rd is hydrogen), or a
thiocarbamoyl chloride
CI-(Xd)-N(Rc)-Rd (wherein Xd is sulfur and with the proviso that neither RC or
Rd is hydrogen),
or a chloroformate, CI-C(Xb)-Xc-Rb (wherein Xb and Xc are oxygen), or a
chlorothioformate Cl-
c(xb) _s,c_
Rb (wherein Xb is oxygen and Xc is sulfur), or a chlorodithioformate CI-C(Xb)-
Xc-Rb
(wherein Xb and Xc are sulfur), or an isothiocyanate, RcN=C=S; or
(c) by sequential treatment with carbon disulfide and an alkylating agent; or
(d) with a phosphorylating agent such as a phosphoryl chloride, CI-P(Xe)(Rf)-
Rg; or
(e) with a sulfonylating agent such as a sulfonyl chloride CI-S02¨Re,
preferably in the
presence of at least one equivalent of base.
Where substituents R4 and R5 are not equal to substituents R6 and R7, these
reactions may
produce, in addition to a compound of formula I, a second compound of formula
(IA).
This invention covers both a compound of formula (I) and a compound of formula
(IA),
together with mixtures of these compounds in any ratio.
X
H, R G, R
3 o Ri
3 0 3 0
R4 R4
G -Z R4
R2 R2
R2
0 0 0
5 6 I
R5 R6
R5 R6
R R G
formula (A) formula I (IA)
The 0-alkylation of cyclic 1,3-diones is known; suitable methods are
described, for example,
by T. Wheeler, US4436666. Alternative procedures have been reported by M.
Pizzorno and
S. Albonico, Chem. Ind. (London), (1972), 425-426; H. Born etal., J. Chem.
Soc., (1953),
1779-1782; M. G. Constantino etal., Synth. Commun., (1992), 22(19), 2859-2864;
Y. Tian et
al., Synth. Commun., (1997), 27 (9), 1577-1582; S. Chandra Roy etal., Chem.
Letters,
(2006), 35(1), 16-17; P. K. Zubaidha etal., Tetrahedron Lett., (2004), 45,
7187-7188.

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The 0-acylation of cyclic 1,3-diones may be effected e.g. by procedures
similar to those
described, for example, by R. Haines, US4175135, and by T. Wheeler, US4422870,
US4659372 and US4436666. Typically diones of formula (A) may be treated with
an
acylating agent preferably in the presence of at least one equivalent of a
suitable base, and
optionally in the presence of a suitable solvent. The base may be inorganic,
such as an alkali
metal carbonate or hydroxide, or a metal hydride, or an organic base such as a
tertiary
amine or metal alkoxide. Examples of suitable inorganic bases include sodium
carbonate,
sodium or potassium hydroxide, sodium hydride, and suitable organic bases
include
trialkylamines, such as trimethylamine and triethylamine, pyridines or other
amine bases
such as 1,4-diazobicyclo[2.2.2]-octane and 1,8-diazabicyclo[5.4.0]undec-7-ene.
Preferred
bases include triethylamine and pyridine. Suitable solvents for this reaction
are selected to
be compatible with the reagents and include ethers such as tetrahydrofuran and
1,2-
dimethoxyethane and halogenated solvents such as dichloromethane and
chloroform.
Certain bases, such as pyridine and triethylamine, may be employed
successfully as both
base and solvent. For cases where the acylating agent is a carboxylic acid,
acylation is
preferably effected in the presence of a known coupling agent such as 2-chloro-
1-
methylpyridinium iodide, N,N'-dicyclohexylcarbodiimide, 1-(3-
dimethylaminopropyI)-3-
ethylcarbodiimide and N,N'-carbodiimidazole, and optionally in the presence of
a base such
as triethylamine or pyridine in a suitable solvent such as tetrahydrofuran,
dichloromethane or
acetonitrile. Suitable procedures are described, for example, by W. Zhang and
G. Pugh,
Tetrahedron Lett., (1999), 40 (43), 7595-7598; T. Isobe and T. Ishikawa, J.
Org. Chem.,
(1999), 64 (19), 6984-6988 and K. Nicolaou, T. Montagnon, G.
Vassilikogiannakis, C.
Mathison, J. Am. Chem. Soc., (2005), 127(24), 8872-8888.
Phosphorylation of cyclic 1,3-diones may be effected e.g. using a phosphoryl
halide or
thiophosphoryl halide and a base e.g. by procedures analogous to those
described by L.
Hodakowski, US4409153.
Sulfonylation of a compound of formula (A) may be achieved e.g. using an alkyl
or aryl
.. sulfonyl halide, preferably in the presence of at least one equivalent of
base, for example by
the procedure of C. Kowalski and K. Fields, J. Org. Chem., (1981), 46, 197-
201.

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Compounds of formula (A), wherein Y is S(0) or S(0)2 may be prepared from
compounds of
formula (A) wherein Y is S by oxidation, e.g. according to a procedure
analogous to that of E.
Fehnel and A. Paul, J. Am. Chem. Soc., (1955), 77, 4241-4244.
A compound of formula (A), wherein Y is 0, S, 0(0) or CR8R9 may be prepared
via the
cyclisation of a compound of formula (B), preferably in the presence of an
acid or base, and
optionally in the presence of a suitable solvent, e.g. by analogous methods to
those
described by T. Wheeler, US4209532. The compounds of the formula (B) have been
particularly designed as intermediates in the synthesis of the compounds of
the formula I.
Compounds of formula (B) wherein R is hydrogen or Cratalkyl, (especially
methyl, ethyl and
tert-butyl) may be cyclised under acidic conditions, preferably in the
presence of a strong
acid such as sulfuric acid, polyphosphoric acid or Eaton's reagent, optionally
in the presence
of a suitable solvent such as acetic acid, toluene or dichloromethane. A
compound of formula
(B) wherein R is alkyl (preferably methyl or ethyl) may also be cyclised under
basic
conditions in the presence of at least one equivalent of a strong base in a
solvent such as
tetrahydrofuran, toluene, dimethylsulfoxide or N,N-dimethylformamide. Suitable
bases
include potassium tert-butoxide, lithium diisopropylamide, sodium
bis(trimethylsilyl)amide or
sodium hydride. A compound of formula (B), wherein R is alkyl, may be produced
from a
compound of formula (B), wherein R is H, by esterification under known
conditions (for
example by treatment with an alcohol, R-OH, in the presence of an acid
catalyst).
0 oR
R3 0 R
acid or base
R,
0 R4
R3 R4R5 R6 solvent
R2
R2
0
R5 R6
formula (B) formula (A)
A compound of formula (B), wherein R is H may be prepared by hydrolysis of a
compound of
formula (C) wherein R is H or alkyl and R' is alkyl (preferably methyl or
ethyl), followed by
acidification of the reaction mixture to effect decarboxylation, e.g. by
similar processes to
those described by, for example, T. Wheeler, US4209532. Alternatively, a
compound of
formula (B), wherein R is alkyl or H may be prepared from a compound of
formula (C),
wherein R' is alkyl (preferably methyl), through a Krapcho decarboxylation
procedure, e.g.
under known conditions using known reagents (see for example G. Quallich, P.
Morrissey,
Synthesis, (1993), (1), 51-53).

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x
oR1
hydrolysis oo Ri
R Y
then acid RKY
R3
or R4R5 R6 R3 R4 R5 R6
R2 R2
CO2 R' Krapcho
decarboxylation
formula (C) formula (B)
A compound of formula (C) wherein R is alkyl may be prepared by treating a
compound of
formula (D) with a suitable carboxylic acid chloride of formula (E) wherein R
is alkyl under
basic conditions. Suitable bases include potassium tert-butoxide, sodium
bis(trimethyl-
silyl)amide and lithium diisopropylamide and the reaction is preferably
conducted in a
suitable solvent (such as tetrahydrofuran or toluene) at a temperature between
-78 C and 30
C. Under similar conditions a compound of formula (C), wherein R is H, may be
prepared
from a suitable anhydride of formula (F).
oR1
base 0
0 Ri
R Y
solvent `0-ji(X-
R'0 R3 R4R5 R6
3 0
R2
o CO2R'R2
R4 5 OR R42)iLio formula (C)
formula (D) y R
R6 or y
')C)
===, R5 R
0 Cl
formula (E) formula (F)
Compounds of formula (E) and formula (F) are known (see, for example T.
Terasawa and T.
Okada, J. Org. Chem., (1977), 42(7), 1163-1169; G. Bennett, W. Houlihan, R.
Mason; R.
Engstrom, J. Med. Chem., (1976), 19 (5), 709-14; L. J. J. Hronowski, Lucjan W.
A. Szarek,
Canadian Journal of Chemistry (1988), 66(1), 61-70; S. F. Birch, V. E. Gripp,
D. T.
McAllan, W. S. Nathan, Journal of the Chemical Society (1952), 1363-8; S.
Kitamura, T. D.
Aicher, Gonzales, Steve; Y. Le Huerou, S. A. Pratt, Y. Nakada, WO 2008011130;
0. Jentzer,
M. Guglieri, WO 2009092795), or may be made by similar methods from
commercially
available starting materials.
Compounds of formula (0), wherein X is methyl and R' is C1-C4alkyl, can be
prepared by
reacting compounds of formula (G) with propyne in the presence of a suitable
catalyst,
optionally a suitable additive, optionally in a suitable solvent at a suitable
temperature.

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Suitable catalysts include transition metal salts or complexes of transition
metal salts (for
example palladium acetate, bis(triphenylphosphine) palladium(II) dichloride,
tetrakis(triphenylphosphine)palladium(0), bis(triphenylphosphine) nickel(11)
dichloride and
tris(acetylacetonato) iron(111)), in an amount typically 0.001-25% with
respect to a compound
of formula (G). Suitable additives include copper salts (for example copper(I)
iodide in an
amount typically 0.001-50% with respect to a compound of formula (G)), and
tetraalkyl
ammonium salts. Suitable bases include diethylamine, triethylamine, piperidine
and
pyrrolidine, and suitable solvents include 1,4-dioxane, N,N-dimethylacetamide
or N,N-
dimethylformamide. Preferably the reaction is carried out using 0.05-10%
bis(triphenylphosphine) palladium(II) dichloride (with respect to a compound
of formula (G)),
0.05-10% triphenylphosphine (with respect to a compound of formula (G)), 0.05-
25%
copper(I) iodide (with respect to a compound of formula (G)), 5-200%
tetrabutyl ammonium
iodide (with respect to a compound of formula (G)), triethylamine and N,N-
dimethylformamide at a temperature between 25 C to 150 C. Such a reaction is
an example
.. of a Sonogashira coupling and similar reactions are known in the literature
(see for example
F. Labrie, S. Gauthier, J. Cloutier, J. Mailhot, S. Potvin, S. Dion, J-Y.
Sanceau, WO
2008124922; M. S. Viciu, S. P. Nolan, Modern Arylation Methods (2009), 183-
220; R.
Chinchilla, C. Najera, Chemical Reviews (2007), 107(3), 874-922;1. P.
Beletskaya, G. V.
Latyshev, A. V. Tsvetkov, N. V. Lukashev, Tetrahedron Letters (2003), 44(27),
5011-5013
.. and J. Mao, G. Xie, M. Wu, J. Guo, S. Ji, Advanced Synthesis & Catalysis
(2008), 350(16),
2477-2482). In an alternative approach a compound of formula (D) may be
prepared from a
compound of formula (G) by reaction with a propynyl transfer reagent such as 1-
propynyllithium, 1-propynylmagnesium bromide, 1-propynylmagnesium chloride, 1-
propynylmagnesium iodide, 1-propynylzinc chloride, 1-propynylzinc bromide, 1-
propynylzinc
iodide, tributylpropynylstannane, 1-propyne-1-boronic acid (or ester thereof),
2-butynoic acid
or 1-(trimethylsilyl)propyne, with a transition metal catalyst system under
suitable conditions
(see for example P. Wessig, G. Mueller, C. Pick, A. Matthes, Synthesis (2007),
(3), 464-477;
J. H. Chaplin, G. S. Gill, D. W. Grobelny, B. L. Flynn, G. Kremmidiotis,
W007087684; A.
Akao, T. Tsuritani, S. Kii, K. Sato, N. Nonoyama, T. Mase, N. Yasuda, Synlett
(2007), (1),
31-36. A. Coelho Coton, E. Sotelo Perez, F. Guitian Rivera, A. Gil Gonzalez,
WO
2011048247; C. H. Oh, S. H. Jung, Tetrahedron Letters (2000), 41(44), 8513-
8516; D. Zhao,
C. Gao, X. Su, Y. He, J. You, Y. Xue, Chemical Communications (2010), 46(47),
9049-9051;
C. Yang, S. P. Nolan, Organometallics (2002), 21(6), 1020-1022). In another
set of preferred
conditions a compound of formula (G) is reacted with 1-propynylmagnesium
bromide in the
.. presence of 0.05-10% bis(triphenylphosphine) palladium(II) dichloride (with
respect to a
compound of formula (G)), in tetrahydrofuran at a temperature between 25 C and
100 C, as

CA 02892076 2015-05-20
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described by J. H. Chaplin, G. S. Gill, D. W. Grobelny, B. L. Flynn, G.
Kremmidiotis, WO
07087684. Compounds of formula (G) are known, or can be prepared by known
methods
using known reagents.
o R1 Hal reagent,
Ri
catalyst, 0
additive
R'0 R'0
solvent,
R2 temperature R2
formula (G) formula (D)
Compounds of formula (0), wherein X is chlorine and R` is Cratalkyl, can be
prepared from
compounds of formula (H) or compounds of formula (I). In one approach a
compound of
formula (H) is first deprotonated with a base such as butyllithium, sodium
hydride, lithium
.. diisopropylamide or ethylmagnesium bromide, then reacted with a chlorine
source such as
N-chloro succinimide, chlorine or carbon tetrachloride. The specific chlorine
source is
selected to provide the required chloro-acetylene. Similar reactions and
conditions are
reported in the literature (see for example M. Tajbakhsh, S. Habibzadeh,
Letters in Organic
Chemistry (2007), 4(7), 512-514; D. Sud, T. J. Wigglesworth, N. R. Branda,
Angewandte
Chemie, International Edition (2007), 46(42), 8017-8019; M. A. P. Martins, D.
J. Emmerich,
C. M. P. Pereira, W. Cunico, M. Rossato, N. Zanatta, H. G. Bonacorso,
Tetrahedron Letters
(2004), 45(25), 4935-4938; A. Poloukhtine, V. Rassadin, A. Kuzmin, V. V.
Popik, Journal of
Organic Chemistry (2010), 75(17), 5953-5962; C. R. Hickenboth, J. D. Rule, J.
S. Moore,
Tetrahedron (2008), 64(36), 8435-8448; F. H. M. Graichen, A. C. Warden, S.
Kyi, M. S.
O'Shea, Australian Journal of Chemistry (2010), 63(4), 719-722; and M. L.
Narayana, M. L.
N. Rao, M. Periasamy, Synthetic Communications (1995), 25(15), 2295-9).
In another approach a compound of formula (D), wherein X is chlorine and R` is
Cratalkyl,
can be prepared from a compound of formula (H) by treatment with a mixture of
reagents
that are known to promote chlorination, such as potassium carbonate,
tetrabutylammonium
bromide and carbon tetrachloride (see for example T. Matsuda, S. Kadowaki, Y.
Yamaguchi,
M. Murakami, Chemical Communications (2008), (24), 2744-2746), pyridine and
chlorine
(see for example R. B. Gutsulyak, V. N. Britsuk, L. A. Kostrikina, Y.
Serguchev, Ukrainskii
Khimicheskii Zhurnal (1993), 59(10), 1062-7), silver nitrate and N-chloro
succinimide, N-
chloro succinimide and hexamethylphosphoramide (see for example G. Pangon, J.
L.
Philippe, P. Cadiot, Comptes Rendus des Seances de l'Academie des Sciences,
Serie C:
Sciences Chimiques (1973), 277(18), 879-81), and/or perchloric acid and acetic
acid (see for

CA 02892076 2015-05-20
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example J. P. Montheard, M. Camps, M. Chatzopoulos, M. 0. A. Yahia, R.
Guilluy, D.
Deruaz, Journal of Chemical Research, Synopses (1983), (9), 224-5). Conditions
are
selected to provide the required chloro-acetylene. When X is chlorine,
preferred conditions
include reacting a compound of formula (H) with 1-5 equivilents of N-chloro
succinimide and
0.05-50% silver acetate (with respect to a compound of formula (H)) in acetone
at a
temperature between 25 C and 100 C.
Compounds of formula (I), wherein IR is Cratalkyl and R" is C1-C4alkyl, can
also be directly
converted to compounds of formula (D), e.g. by treatment with isocyanuric
chloride or N-
chloro succinimide and silver nitrate (see for example M. H. Vilhelmsen, A. S.
Andersson, M
B. Nielsen, Synthesis (2009), (9), 1469-1472).
X
oRi
SiR",
o Ri
o Ri
reagent reagent
R
R'0 _____________________ 3 R'0
solvent, solvent, '0
R2 temperature R2 temperature R2
formula (H) formula (D) formula (I)
A compound of formula (I), wherein R' is C1-C4alkyl and R" is Cratalkyl, can
be prepared by
reacting a compound of formula G with a trialkylsilylacetylene, under similar
conditions
described previously to convert a compound of formula (G) to a compound of
formula (D)
(wherein X is methyl).
A compound of formula (H) can either be prepared by deprotection of a compound
of formula
(I), e.g. under known conditions, or by reacting a compound of formula (G)
with an ethynyl
transfer reagent such as tributylstannylacetylene, lithium acetylide
ethylenediamine complex,
ethynylzinc bromide or ethynylmagnesium chloride in the presence of a suitable
catalyst
system, e.g. under conditions similar to those described previously (see for
example C.
Fischer, J. Methot, H. Zhou, A. J. Schell, B. Munoz, A. A. Rivkin, S. P.
Abeam, S. Chichetti,
R. N. Maccoss, S. D. Kattar, M. Christopher, C. Li, A. Rosenau, W. C. Brown,
WO
2010071741; M. Behler, A. Eluntlaut, C. Ferman, A. Chapuf, CN 101195641; G.
Wang, G.
Zhu, E. Negishi, Journal of Organometallic Chemistry (2007), 692(21), 4731-
4736 and E.
Negishi, M. Kotora, C. Xu, Journal of Organic Chemistry (1997), 62(25), 8957-
8960).

CA 02892076 2015-05-20
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H ,
o Ri
o Ri Hal
reagent reagent 0 Ri
R'0 R'0
catalyst, catalyst, R'0
R2 solvent, R2 solvent, R2
temperature temperature
formula (H) formula (G) formula (I)
A
deprotection
In a further approach, a compound of formula (D) (wherein X is chlorine) can
either be
prepared from a compound of formula (J) or a compound of formula (K), by
treatment with a
suitable base, in a suitable solvent, at a suitable temperature. A compound of
formula (J)
can be converted to a compound of formula (D) under conditions similar to
those described
in the literature, for example treatment using potassium tert-butoxide in tert-
butanol at a
temperature between 25 C and 150 C, or lithium 2,2,6,6-tetramethylpiperidine
in
tetrahydrofuran at a temperature between -25 C and 50 C (see for example E.
Bartmann, R.
Hittich, H. Plach, U. Finkenzeller, U55188759 and Indian Journal of Chemistry,
Section B:
Organic Chemistry Including Medicinal Chemistry, 1978, vol. 16, 1051-1054). A
compound of
formula (K) can also be converted to a compound of formula (D) under
conditions similar to
those described in the literature, for example by treatment with cesium
carbonate in N,N-
dimethylformamide at a temperature between 25 C and 150 C, sodium tert-
butoxide in
toluene at a temperature between 25 C and 150 C, 1,8-diazabicyclo[5.4.0]undec-
7-ene in
dimethylsulfoxide at a temperature between 0 C and 50 C, or potassium tert-
butoxide in
tetrahydrofuran at a temperature between -78 C and 25 C (see for example B. C.
G.
Soederberg, S. P. Gorugantula, C. R. Howerton, J. L. Petersen, S. W. Dantale,
Tetrahedron
(2009), 65(36), 7357-7363; S-C. Lo, R. E. Harding, E. Brightman, P. L. Burn,
I. D. W.
Samuel, Journal of Materials Chemistry (2009). 19(20), 3213-3227; S. Wang, T.
Kohn, Z. Fu,
X. Y. Jiao, S. Lai, M. Schmitt, Tetrahedron Letters (2008), 49(51), 7284-7286
and M. L. G.
Borst, R. E. Bulo, D. J. Gibney, Y. Alem, F. J. J. de Kanter, A. W. Ehlers, M.
Schakel, M.
Lutz, A. L. Spek, K. Lammertsma, Journal of the American Chemical Society
(2005),
127(48), 16985-16999). Compounds of formula (J) and (K) (wherein X is
chlorine) can be
prepared from known compounds using known methods and reagents.

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o Ri X
0 Ri
X 0 base
X
R'
solvent,
R2
temperature R2
formula (J) formula (D)
base
solvent,
temperature
X
0 Ri
R'0 X
R2
formula (K)
In a further approach a compound of formula (A), wherein X is methyl, can be
prepared
directly from a compound of formula (L), under similar conditions described
previously to
convert a compound of formula (G) to a compound of formula (D).
oRi Hal
Açr
3 0 R 1
reagent
R4
temperat R4
solvent,
R2 ure R2
0 0
R5 R6 R5 R6
formula (L) formula (A)
A compound of formula (L) can be prepared from a compound of formula (G) using
similar
procedures to those outlined previously.

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Hal
Ri Hal
Ri 0 0
0 acylation R Y
RO R3 R4R5 R6 CO2R'R2
R2
formula (G) formula (N)
ihydrolysis and
decarboxylation
H, Ri Hal
3
R
0 Hal
R cyclisation 0 O1
R4 ...
'''' R,o,y
Y R2
0 R3 R4R5 R6 R2
R5 R6
formula (L) formula (M)
A compound of formula (A), wherein X is chlorine, can be prepared from a
compound of
formula (L), via either a compound of formula (0) or a compound of formula (P)
(wherein R"
is Cratalkyl), e.g. under similar conditions to those described previously.
Si R"3
.-'
R1 Hal
R3 0
R4
/
3 0 R1
reagent R
R4_õ...
solvent,
Y R2
temperature Y R2
0 0
R5 R6 R5 R6
formula (L) formula (P)
reagent, 1
1 reagent,
solvent, solvent,
temperature
temperature
H X
../
R3 0 R1 /
3 0
R
reagent
R4
Y R2 solvent,
Y
0 temperature 0
R5 R6 R5 R6 R2
formula (0) formula (A)

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A compound of formula (A), wherein X is chlorine, can also be prepared from a
compound of
formula (Q), e.g. under conditions similar to those described for converting a
compound of
formula (K) to a compound of formula (D).
o
R3 OR1
base
R4 X
R4
solvent,
R2
R2
0 temperature
0
R5 R6 R5 R6
formula (Q) formula (A)
A compound of formula (Q), wherein X is chlorine may be prepared from an
aldehyde of
formula (R) by treatment with triphenylphosphine in the presence of carbon
tetrachloride in a
suitable solvent at a suitable temperature. Carbon tetrachloride is selected
to provide the
required dichloroalkene, and similar reactions are known in the literature
(see for example A.
Poloukhtine, V. V. Popik, Journal of the American Chemical Society (2007),
129(40), 12062-
12063; L. N. Michaelides, B. Darses, D. J. Dixon, Organic Letters (2011),
13(4), 664-667
and F. Gavina, S. V. Luis, P. Ferrer, A. M. Costero, J. A. Marco, Journal of
Chemical
Research, Synopses (1986), (9), 330-1).
X
R3 0 Ri
3 OR1
reagent
X
R4
R4
solvent,
R2 R2
0 temperature
0
R5 R6 R5 Re
formula (R) formula (Q)
A compound of formula (R) may be prepared by the formylation of a compound of
formula (L)
(wherein Hal is chlorine, bromine or iodine, preferably bromine or iodine).
Suitable conditions
for effecting the formylation of aryl halides are known, and include, for
example, the
treatment of an aryl halide with a suitable organometallic reagent (such as
isopropyl
magnesium chloride, n-butyllithium, sec-butyllithium or tert-butyllithium), or
by treatment with
a suitable alkali metal or alkali earth metal (such as lithium or magnesium)
in a suitable
solvent (such as diethyl ether, dimethoxyethane or tetrahydrofuran). The
resulting arylmetal
reagent is then reacted with a suitable formylating agent such as N,N-
dimethylformamide or
N-formylmorpholine. Alternatively a compound of formula (R) may be prepared
from a

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compound of formula (L) (wherein Hal can also be a pseudohalogen such as
triflate) by
treatment with a carbonylating agent (such as carbon monoxide) in the presence
of a
suitable catalyst system, base, and reducing agent (see for example L.
Ashfield and C.
Barnard, Org. Process Res. Dev., 11(1), 39 -43, 2007).
Hal
o Ri
R3 0 Ri
formylation
R4 R4
R2 R2
0
R5 R6 R5 R6
formula (L) formula (R)
In an alternative approach a compound of formula I, wherein X is methyl and G
is preferably
methyl of ethyl, may be prepared from a boronic acid or boronic ester of
formula (S) (as
shown below) by treatment with either 1-bromo-1-propyne or 1-iodo-1-propyne,
preferably in
the presence of a suitable catalyst system, a suitable base and/or a suitable
solvent and/or at
a suitable temperature. Similar reactions are known in the literature, and
preferred
conditions involve reacting a compound of formula (S) with 1-iodo-propyne in
the presence of
0.005-25% palladium(II) chloride (with respect to a compound of formula (S))
and 1-10
equivalents potassium carbonate, preferably in a mixture of toluene, water and
methanol at a
temperature between 50 C-150 C, as described by Y. Shi, X. Li, J. Liu, W.
Jiang, L. Sun,
Tetrahedron Letters (2010), 51(28), 3626-3628. A compound of formula (T),
wherein G is
preferably methyl of ethyl and R" is C1-C4alkyl, may be prepared under similar
conditions
using either 1-bromo-2-(trimethylsilyl)acetylene or 1-iodo-2-
(trimethylsilyl)acetylene as the
coupling partner. Compounds of formula (A) and (P) may be prepared from
compounds of
formula I and (T) respectively, by hydrolysis of the enol ether.

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Si R"3
SiR"3 OR
1 I G, Ri B.,
G, Ri
3 0 OR
R5
4
3 0
R R
Hal
R ..,
....,_ R4
Y R2
catalyst, Y R2
0 base, 0
R6 solvent R5 R6
formula (T)
formula (S)
X
hydrolysis 1
I catalyst,
base,
solvent
Hal
Si
R"3 X
4R1 /
.H/ G,
3 0 3 0
R R
R R4 ==
Y R2 Y R2
0 0
R5 R6 R5 R6
formula (P) formula I
Ihydrolysis
X
R1 ,2.-
3 0
R
R4
Y R2
0
R5 R6
formula (A)
In one approach a compound of formula (S) may be prepared from a compound of
formula
(L) (wherein Hal is preferably iodine or bromine), preferably by treatment
with a suitable base
(such as sodium hydride, potassium hydride or isopropylmagnesium chloride), in
a suitable
solvent (such as tetrahydrofuran or diethyl ether), followed by a metal-
halogen exchange
reaction (preferably by treatment with an alkyllithium reagent such as n-
butyllithium, sec-
butyllithium or tett-butyllithium, or an organomagnesium reagent such as
isopropyl

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magnesium chloride) and subsequent treatment with a trialkylborate, B(OR")3,
(preferably
trimethylborate) to give the corresponding boron ate ester of formula (S).
OR OH
1-1,0R1 Hal H, Ri B, H, Ri B,
0 OR
3 0 OH
IRT
1. R R4
base4
_______________________________________________________ R4
R2 2. R-Li, solvent R2 hydrolysis R2
0 0
R5 R6 R5 R6 R5 R6
formula (L)
formula (S)
In an alternative approach a compound of formula (U) may be prepared from a
compound of
formula (V), wherein G is preferably methyl or ethyl, by C-H borylation with a
suitable
borylating agent, a suitable catalyst system, in a suitable solvent at a
suitable temperature.
Suitable catalysts include 1,5-cyclooctadiene)(methoxy)iridium(1) dimer in
combination with
4,4'-di-tert-butyl-2,2'-dipyridyl, suitable borylating agents include
bis(pinacolato)diboron or
pinacol borane, and suitable solvents include hexane, octane, tetrahydrofuran
and methyl
tert-butyl ether. Similar examples are known in the literature (see for
example J. F. Hartwig,
Chemical Society Reviews (2011), 40(4), 1992-2002 and T. lshiyama, N. Miyaura,
Pure and
Applied Chemistry (2006), 78(7), 1369-1375). Preferred conditions include
treating a
compound of formula (V) with 0.05-10% 1,5-cyclooctadiene)(methoxy)iridium(1)
dimer (with
respect to a compound of formula (V)), 0.05-10% 4,4'-di-tert-butyl-2,2'-
dipyridyl (with respect
to a compound of formula (V)), and 1-2 equivalents bis(pinacolato)diboron
(with respect to a
compound of formula (V)) in methyl tert-butyl ether at a temperature between
50 C -150 C,
optionally under microwave irradiation, as described by P. Harrisson, J.
Morris, T. B. Marder,
P. G. Steel, Organic Letters (2009), 11(16), 3586-3589.
OR
G, RI
BI
Ri
0 OR
reagent
R4
R4
R2 catalyst,
0 solvent R2
0
R5 R6 temperature
R5 R6
formula (V) formula (U)
Compounds of formula (W) can be prepared from compounds of formula (X) using
similar
25 procedures described above, starting from compounds of formula (Z) which
are known
compounds.

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o Ri 0 OR1
acylation R Y
RO R3 R4R5 R6 CO2R'R2
R2
formula (Z) formula (Y)
1
hydrolysis and
decarboxylation
H, Ri
3 0
R cyclisation 0 0 Ri
R4 -,.
"'"-
Y R2
0 IR3 R4R5 R6 R2
R5 R6
formula (W) formula (X)
In a further approach a compound of formula (A), wherein Xis methyl, may be
prepared via
the rearrangement of a compound of formula (AA), in the presence of a reagent
which
promotes rearrangement, such as a metal alkoxide (preferably in an amount
equal to or
greater than 100% with respect to compound of formula (AA)) or cyanide anion
(for example
0.001-25% potassium cyanide or 0.001-25% sodium cyanide with respect to a
compound of
formula (AA)), or a cyanohydrin (preferably 0.001-25% acetone cyanohydrin with
respect to a
compound of formula (AA)). This reaction is preferably performed in a suitable
solvent at a
suitable temperature (typically 25-150 C). Preferably a compound of formula
(AA) is treated
with 1-3 equivalents of sodium methoxide in N, N-dimethylformamide at a
temperature
between 50 C and 100 C.
x
/
R
R4RILOR1
reagent
solvent, 25 C to 1500C Y R2
R5 R5 R2 0
R5 R6
formula (AA)
formula (A)
In one approach a compound of formula (AA), wherein X is methyl, may be
prepared from a
compound of formula (AB) by treatment with a catalyst system which promotes
lactonisation
(such as palladium(II) dichloride, gold(I) chloride or silver carbonate),
preferably 0.001-50%
silver carbonate with respect to compound of formula (AB), in the presence of
a suitable

CA 02892076 2015-05-20
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solvent (for example acetonitrile) at a suitable temperature (typically 25 C
to 150 C), and
optionally under microwave irradiation. Similar lactonisations are known in
the literature (see
for example WO 2008/071405, P. Huang and W. Zhou, Tetrahedron Asymmetry
(1991), 2
(9), 875-878; and H. Harkat, J-M. Weibel, P. Pale, Tetrahedron Letters (2006),
47(35), 6273-
6276).
R1
CO2H catalyst, solvent R4ROR1
R4
Y
Y 25 C to 100 C
R2 R5 R6
R2
R5 R6
formula (AB) formula (AA)
Compounds of formula (AB) can be prepared from compounds of formula (AD) and
compounds of formula (AE) (wherein R"` is preferably C1-C4alkyl), via
compounds of formula
(AC), by methods analogous to those described in WO 2008/071405. Alkynes of
formula
(AD) are known or can be prepared by known methods (see for example WO
2008/071405
and references therein, and J. P. Burke, M. Sabat, D. A. lovan, W. H. Myers,
J. J. Chruma,
Organic Letters (2010), 12(14), 3192-3195). Compounds of formula (AE) are
either known
compounds or can be prepared from known reagents using known methods.
X
R
Hal
R2 X
R
3 formula (AE)
R1
CO,R'"
R3
R¨Y H y.0O2R¨
Sonogashira
Y
R5 R6 catalyst R2
base, solvent R5 R6
formula (AD) formula (AC)
hydrolysis
X
R1
R3
Y
R2
R5 R6
formula (AB)

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A compound of formula (P), wherein R" is C1-C4alkyl, can also be prepared
using similar
chemistry to that described previously, starting with a compound of formula
(AD) and a
compound of formula (Al) which are both known in the literature or can be
prepared using
known methods and known reagents.
/
Ri /-
Hal
R2 SiR",
/
CO2R formula (Al)
"' H R4C0 R'
R R4 2
Son ogashira
R5 R6 catalyst
R5 R6 R2
base, solvent
formula (AD) formula (AH)
hydrolysis
I
SiR",
0 Si R"3 R i
/'
R 4A-0 R4RY 2
catalyst, solvent
R2
25 C to 100 C
R5 R6 R2 R5 R6
formula (AG)
formula (AF)
1
reagent
solvent, 25 C to 150 C
Si R"3
,'-
H, R1 /
R
R4 \
Y R2
0
R5 R6
formula (P)
10 Similarly, a compound of formula (L) can be prepared from a compound of
formula (AJ) using
similar chemistry to that described previously.

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R1 101 Hal
Hal
R2
Ri Hal
R3 H formula (AN)
R4
' - X.,CO2R"'
R4R3
Sonogashira
R5 R6 catalyst
R5 R6 R2
base, solvent
formula (AD) formula (AL)
hydrolysis
I
o R1 Hal
R4Ai R3
Ri Hal 44,CO21-1
R4 0 R
catalyst, solvent
Y =õ Y --
R2
25 C to 100 C
R5 R5 R2
R5 R6
formula (AK)
formula (AJ)
1
reagent
solvent, 25 C to 150 C
H, R1 Hal
3 0
R
R4
Y R2
o
R5 R6
formula (L)
Similarly, a compound of formula (W) can be prepared from a compound of
formula (AO)
using similar chemistry to that described previously.

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R1 0
Hal
R2
i
formula (AR) R
RH
14CO2R'"
RrCO R'
2.,
Sonogashira R4
Yy-
_______________________________________ ..
R2
R5 R6 catalyst
base, solvent R5 R6
formula (AD) formula (AQ)
hydrolysis
V
0 Ri
p3
RXI R4'L\rCO2H
catalyst, solvent /
25 C to 100 C R2
R5 R6 R2 R5 R6
formula (AO) formula (AP)
Ireagent
solvent, 25 C to 150 C
H, Ri
, 0
R
R4
Y
0 R2
R5 R6
formula (\A)
In a second approach a compound of formula (AA), wherein X is methyl, may be
prepared
via the Baeyer-Villiger oxidation of a compound of formula (AS), preferably in
a suitable
solvent and/or at a suitable temperature (e.g. from 0 C to 100 C), and
optionally in the
presence of a suitable catalyst system. Suitable oxidants include peracetic
acid and
hydrogen peroxide. Preferred conditions are hydrogen peroxide and catalytic
selenium
dioxide (0.001-25m01%) in tert-butanol at a temperature of from 0 C to 100 C,
as described
by J. A. Guzman, V. Mendoza, E. Garcia, C. F. Garibay, L. Z. Olivares, L. A.
Maldonado,
Synthetic Communications (1995), 25(14), 2121-33.

CA 02892076 2015-05-20
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x
0
Ry
0 oxidant, solvent R4L 0
R3
R2
R4
R5 Re R2
R5 Re
formula (AA)
formula (AS)
A compound of formula (AS), wherein X is methyl, may be prepared from a
compound of
formula (AU) by condensation with a benzaldehyde of formula (AT), in the
presence of a
suitable base and optionally in the presence of a suitable solvent (for
similar examples see
WO 2010136431; A. Lagrange, S. Forestier, G. Lang and B. Luppi, EP368717 A1;
D. C.
Rowlands, US2776239; E. Tamate, Journal of the Chemical Society of Japan,
(1957), 78,
1293-7; R. Hernandez, D. Melian, T. Prange, E. Suarez, Heterocycles (1995),
41(3), 439-54;
and J. Sotiropoulos, N. El Batouti, A. M. Lamazouere, Journal of Heterocyclic
Chemistry
(1987), 24(4), 907-12).
R1
o R1
ase
R4 +
R2
R6 sbolvent
R4
R5 H R2 R6
R5
formula (AU) formula (AT)
formula (AS)
Preferably the base is a metal hydroxide, such as sodium hydroxide or
potassium hydroxide,
metal alkoxide such as sodium methoxide, sodium ethoxide or potassium tert-
butoxide, or
metal amide such as sodium amide. Preferably the solvent is dimethoxyethane,
dioxane,
tetrahydrofuran, diethyl ether or an alkyl alcohol, such as methanol, ethanol
or isopropanol.
Compounds of formula (AU), wherein Y is 0 and or CR8R9, are known compounds
(see for
example X. Ye, M. D. Johnson, T. Diao, M. H. Yates, S. S. Stahl, Green
Chemistry (2010),
12(7), 1180-1186; M. Newman and W. Reichle, Org. Synth. Coll. Vol. V., (1973),
1024; Y.
Zal'kind, E. Venus-Danilova and V. Ryabtseva, Russian Journal of General
Chemistry,

CA 02892076 2015-05-20
WO 2014/096289 PCT/EP2013/077541
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(1950), 20, 2222-9; M. Bertrand, J. Dulcere, G. Gil, J. Grimaldi and P.
Sylvestre-Panthet,
Tetrahedron Letters (1976), (18), 1507-8), or may be prepared from known
compounds by
known methods.
Compounds of formula (AU), wherein Y is C(0), are known compounds (see for
example N.
J. Turro, D. R. Morton, E. Hedaya, M. E. Kent, P. D'Angelo, P. Schissel,
Tetrahedron Letters
(1971), (27), 2535-8; P. A. Krapcho, D. R. Rao, M. P. Si!von, B. Abegaz,
Journal of Organic
Chemistry (1971), 36(25), 3885-90; S. N. Crane, T. J. Jenkins, D. J. Burnell,
Journal of
Organic Chemistry (1997), 62(25), 8722-8729; S. N. Crane, D. J. Burnell,
Journal of Organic
Chemistry (1998), 63(4), 1352-1355; S. N. Crane, D. J. Burnell, Journal of
Organic Chemistry
(1998), 63(16), 5708-5710; C. E. Elliott, D. 0. Miller, D. J. Burnell, Journal
of the Chemical
Society, Perkin Transactions 1 (2002), (2), 217-226), or may be prepared from
known
compounds by known methods.
Compounds of formula (AU), wherein Y is S, S(0) or S(0)2 are known compounds
(see for
example E. R. Buchman, H. Cohen, Journal of the American Chemical Society
(1944), 66,
847-8; A. W. D. Avison, F. Berge!, J. W. Haworth, U52408519: K. G. Mason, M.
A. Smith, E.
S. Stern, EJ. A. Elvidge, Journal of the Chemical Society [Section] C: Organic
(1967), (21),
2171-6; T. A. Magee, Thomas A. DE 2033454; I. Tabushi, Y. Tamaru, Z. Yoshida,
T.
Sugimoto, Journal of the American Chemical Society (1975), 97(10), 2886-91; P.
E. Aldrich,
G. H. Berezin, B. I. Dittmar, I. Bruce, DE 2516554; I. Tabushi, Y. Tamaru, Z.
Yoshida,
Bulletin of the Chemical Society of Japan (1978), 51(4), 1178-82; D. N.
Reinhoudt, J.
Geevers, W. P. Trompenaars, S. Harkema, G. J. Van Hummel, Journal of Organic
Chemistry
(1981), 46(2), 424-34; F. Duus, Synthesis (1985), (6-7), 672-4; J. Schatz,
Science of
Synthesis (2002), 9, 287-422), or may be prepared from known compounds by
known
methods.
A compound of formula (AT), wherein X is methyl, can be prepared from known
compounds
by known methods.
A compound of formula (P), wherein R" is Cratalkyl, can also be prepared from
a compound
of formula (AF), by rearrangement under conditions similar to those described
for the
conversion of a compound of formula (AA) to a compound of formula (A). A
compound of
formula (AW) is known, or can be prepared by known methods using known
reagents.

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SiR"3
R_3..
base OR1
R4 SIR", + R1
Y
, R5 solvent --
R- 0 R2 R R24
Y
H 5 R5
formula (AU) R
formula (AVV)
formula (AV)
ioxidant
solvent
SiR", 0 SiR",
/
/
3 0 reagent, base R 0
R
solvent, 25 C to 100 C
Y R2 R5 R6
R2
0
R5 R6
formula (AF)
formula (P)
Similarly, a compound of formula (L) can also be prepared from a compound of
formula (AJ)
by rearrangement under similar conditions. Compounds of formula (AY) are known
compounds, or can be prepared from known reagents using known methods.

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Hal
0 Hal
R.Z.y. R
ase 0 1
R4 Ri
Y 2
5 R6 soblvent _--
R- 0 R2 R4 R
Y
H 5 R6
formula (AU) R
formula (AY)
Iformula (AX)
oxidant
solvent
0
H, Ri Hal
3 0 reagent, base R4R0R1 Hal
R
solvent, 25 C to
R4 100C == Y
, _________
Y R2 R5 R6 R2
0
R5 R6
formula (AJ)
formula (L)
Similarly, a compound of formula (W) can also be prepared from a compound of
formula
(AO) by rearrangement under similar conditions. Compounds of formula (AAA) are
known
compounds, or can be prepared from known reagents using known methods.
o
R3 R1
0
R4----\ + R1 base 40 R3
Y R- , H R6 0 R2 solvent
R5
R4 -- R2
Y
5
formula (AU) formula (AAA) R
formula (AZ)
ioxidant
solvent
H, Ri 0
3 0 4R 0 R
R reagent, base
R-1.3 1
R4 solvent, 250C to 1000C
Y R2
0 R5 R6 R2
R5 R6
formula (AO)
formula (W)

CA 02892076 2015-05-20
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In a further approach, a compound of formula (A), wherein X is methyl, can be
prepared by a
rearrangement of an epoxide of formula (AAB) catalysed by the presence of an
acid, e.g. in
the presence of a suitable solvent.
H, Ri
Ri acid, e.g. 0
0 protic acid or
R3 0 Lewis acid R4
R2
R4 R2
0
R5 R6
R5
formula (AAB) formula (A)
For the rearrangement of (AAB) to (A), suitable acids include a BrOnsted acid
such as a
mineral acid or an organic acid, for example sulfuric acid, hydrochloric acid,
hydrogen
chloride, p-toluenesulfonic acid, methanesulfonic acid, acetic acid or formic
acid, or a Lewis
acid such as a metal halide, for example boron trifluoride, aluminium
chloride, iron chloride,
tin(IV) chloride, zinc chloride, zinc bromide, or lithium perchlorate, or a
metal triflate such as
scandium triflate or ytterbium triflate. Mixtures of such acids can also be
used. The
conversion of a compound of formula (AAB) into a compound of formula (A) may
be
considered to be an example of a semi-Pinacol rearrangement (see for example
WO
2010136431; M. Paulson, M. Daliya and C. Asokan, Synth. Commun. (2007), 37(5),
661-
665; S. Sankararaman and J. Nesakumar, J. Chem. Soc, Perkin Trans. 1, (1999),
(21), 3173-
3175; K. Rehse and R. Bienfait, Archiv der Pharmazie, (1984), 317(5), 385-93;
H. Kamath, A.
Sahasrabudhe, B. Bapat and S. Kulkarni, Indian J. Chem., Section B: (1981),
20B(12), 1094-
6; G. Buchanan and D. Jhaveri, J. Org. Chem. (1961), 264295-9; and H. House,
Richard L.
Wasson, J. Am. Chem. Soc., (1956), 78, 4394-400). For the rearrangement of
(AAB) to (A),
a suitable solvent is generally a solvent chosen to be compatible with the
acid used, and
include a chlorinated hydrocarbon, an alcohol, an ether, an aromatic solvent
or an organic
acid, for example dichloromethane, dichloroethane, diethyl ether, acetic acid,
formic acid,
toluene, benzene, methanol, ethanol, isopropanol or tetrahydrofuran.
Preferably the reaction
is performed using methanesulfonic acid in toluene at a temperature between 25
C and
150 C.

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A compound of formula (AAB) can be prepared by the epoxidation of a compound
of formula
(AS). Epoxidation may be effected by treatment of a compound of formula (AS)
with a
suitable oxidising agent such as an organic peroxide or metal hyperchlorite,
for example
dimethyldioxirane, sodium hypochlorite, hydrogen peroxide, tert-butyl peroxide
or
trifluoroperacetic acid, optionally in combination with a suitable base (such
as an alkali metal
hydroxide or carbonate, alkaline earth metal hydroxide or carbonate, or an
amine base such
as 1,8-diazabicyclo[5.4.0]-undec-7-ene), optionally in a suitable solvent
(such as an alcohol
or halogenated hydrocarbon, for example methanol, ethanol or dichloromethane)
and at a
suitable temperature. The reaction can also be performed under biphasic
conditions, in which
a phase-transfer reagent is also typically used in 0.001-50 mol%. The phase
transfer reagent
is preferably a quaternary ammonium salt, a crown ether, a polyethylene
glycol, or
phosphonium salt. Similar reactions are known in the literature (see for
example WO
2010136431; I. K. Korobitsyna, 0. P. Studzinskii, The Russian Journal of
Organic Chemistry
(1969), 5(8), 1493-5; A. Halasz, Z. Jambor, A. Leval, C. Nemes, T. Patonay and
G. Toth, J.
Chem. Soc, Perkin Trans. 1, (1996), (4), 395-400; N. Yousif, F. Gad, A. Fahmy,
M. Amine
and H. Sayed, Phosphorus, Sulfur and Silicon and the Related Elements (1996),
117, 11-19;
T. Ooi, D. Ohara, M. Tamura and K. Maruoka, J. Am. Chem. Soc., (2004),
126(22), 6844-
6845; A. Amr, H. Hayam and M. Abdulla, Archiv der Pharmazie, (2005), 338(9),
433-440; K.
Drauz, S. M. Roberts, T. Geller and A. Dhanda, U56538105 BI; and L. S.
Chagonda and B.
A. Marples, J. Chem. Soc. Perkin 1, 1988, 875-879). Preferably, epoxidation is
carried out
using hydrogen peroxide and a metal hydroxide (especially lithium hydroxide or
sodium
hydroxide), in methanol at a temperature of between -10 C and 60 C.
// //
R1
o Ri
R3
R R3 0
R2 R2
4
oxidant solvent R4
R6 R6
R5 R5
formula (AS) formula (AAB)
Alternatively a compound of formula (AAB), wherein X is methyl, may be
prepared by
reacting a compound of formula (AAC) (wherein halogen is chlorine, bromine or
iodine,
preferably chlorine or bromine) with a compound of formula (AT), in the
presence of a
suitable base, optionally in a suitable solvent, at a suitable temperature.

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Ri
R3 Hal 0 Ri base
R4 +
solvent R2
R6
H R2 R4
R5
R6
formula (AAC) formula (AT) R5
formula (AAB)
Suitable bases include alkali or alkali earth metal hydroxides (such as sodium
hydroxide,
lithium hydroxide or potassium hydroxide), alkali or alkali earth metal
alkoxides (such as
sodium methoxide, sodium ethoxide, potassium tert-butoxide or sodium tert-
butoxide), alkali
or alkali earth metal carbonates (such as potassium carbonate or sodium
carbonate, or
sodium bicarbonate), metal amides (such as lithium diisopropylamide, lithium
hexamethyldisilazide or lithium 2,2,6,6-tetramethylpiperidide),
organometallics (such as butyl
lithium or ethylmagnesium bromide) or metal hydrides (such as sodium hydride
or potassium
hydride). Suitable solvents include chlorinated hydrocarbons, ethers,
alcohols, aromatics and
various polar aprotic solvents, for example 1,2-dimethoxyethane,
tetrahydrofuran, 1,4-
dioxane, diethyl ether, dibutyl ether, dichloromethane, dichloroethane,
acetonitrile, dimethyl
sulfoxide, N, N-dimethylformamide, benzene, toluene, methanol, ethanol,
isopropanol or tert-
butanol, and is chosen to be compatible with the base under the reaction
conditions. The
reaction can also be performed under biphasic conditions, in which a phase-
transfer reagent
is also typically used in 0.001-50 mol /0. The phase transfer reagent is
preferably a
quaternary ammonium salt, a crown ether, a polyethylene glycol, or phosphonium
salt. Most
preferably the reaction is performed using lithium diisopropylamide in
tetrahydrofuran at a
temperature range of -100 C to 60 C. The conversion of a compound of formula
(AAC) into a
compound of formula (AAB) may be considered to be an example of a Darzens
condensation
(see for example WO 2010136431; W. N. Wassef, M. M. El-Barky, Journal of
Chemical
Research, Synopses (1990), (12), 402-3; J. Li, X. Liu, X. Li, Youji Huaxue
(2007), 27(11),
1428-1431; Y. Tong, Y. Cheng, X. Guo, S. Wu, Hecheng Huaxue (2007), 15(1), 102-
104; C.
Parmenon, J. Guillard, D. Caignard, N. Hennuyer, B. Staels, V. Audinot-
Bouchez, J. Boutin,
C. Dacquet, A. Ktorza, M. Viaud-Massuard, Bioorganic & Medicinal Chemistry
Letters (2008),
18(5), 1617-1622; H. Xiao, X. Han, J. Xiong, Faming Zhuanli Shenqing Gongkai
Shuomingshu (2007), p11; J. M. Concellon, E. Bardales, R. Llavona, Journal of
Organic
Chemistry (2003), 68(4), 1585-1588).

CA 02892076 2015-05-20
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Compounds of formula (AAC), wherein Y is 0 or CR8R9 are either known compounds
(see
for example WO 2010136431; B. Sreedhar, P. S. Reddy, M. Madhavi, Synthetic
Communications (2007), 37(23), 4149-4156; R. R. AganNal, S. S. Deshapande,
Journal of
the Indian Chemical Society (1949), 26, 483-6; H. Richet, R. Dulou, R., G.
Dupont, Bulletin
de la Societe Chimique de France (1947), 693-9; H. Richet, Ann. Chim. [12]
(1948), 3 317-
54; I. K. Korobitsyna, Yu. K. Yur'ev, Yu. A. Cheburkov, E. M. Lukina, Russian
Journal of
General Chemistry (1955), 25, 734-8; I. K. Korobitsyna, Yu. K. Yur'ev, Yu. A.
Cheburkov, E.
M. Lukina, Russian Journal of General Chemistry (1955), 25, 690-702; F.
Leonard, A.
Wajngurt, H. Horn, Journal of Organic Chemistry (1956), 21, 1400-4; I. K.
Korobitsyna, I. G.
Zhukova, V. A. Kuvshinova, N. N. Gaidamovich, Yu. K. YuCev, Doklady Akademii
Nauk
SSSR (1957), 114, 327-30; I. K. Korobitsyna, I. G. Zhukova, I. G, Yu. K.
Yur'ev, Russian
Journal of General Chemistry (1959), 29, 2190-6; I. K. Korobitsyna, L. L.
Rodina, L. M.
Stashkova, Chemistry of Heterocyclic Compounds (1966), (6), 843-7; G. Hoehne,
F.
Marschner, K. Praefcke, P. Weyerstahl, Chem. Ber. (1975), 108(2), 673-82; H.
Saimoto, T.
Hiyama, H. Nozaki, Bull. Chem. Soc. Jpn., (1983), 56(10), 3078-87; A. M.
Zvonok, N. M.
Kuz'menok, I. G. Tishchenko, L. S. Stanishevskii, Russian Journal of General
Chemistry
(1985), 21(6), 1330-4) or can be prepared from compounds of formula (AU) under
known
conditions.
Compounds of formula (AAC), wherein Y is S, 5(0) and S(0)2, are either known
compounds
(see for example M. Polievka, L. Uhlar, V. Patek, Petrochemia (1973), 13(5-6),
156-60; N. N.
Novitskaya, B. V. Flekhter, G. M. Prokhorov, A. S. Lukmanova, G. A. Tolstikov,
G. V.
Leplyanin, S. A. Lange, M. V. Strashnov, SU 468920 Al; P. H. McCabe, W.
Routledge,
Tetrahedron Letters (1976), (1), 85-6; T. S. Chou, C. Y. Tsai, Tetrahedron
Letters (1992),
33(29), 4201-4), or can be prepared from compounds of formula (AU) under known
conditions. Compounds of formula (AAC), wherein Y is C(0), can be prepared
from
compounds of formula (AU) under similar halogenation conditions.
Compounds of formula (P), wherein R" is C1-C4alkyl, can also be prepared from
compounds
of formula (AAD), using similar procedures and conditions described
previously. Compounds
of formula (AAD) can either be prepared from compounds of formula (AU) and
(AW), via
compounds of formula (AV), or from compounds of formula (AAC) and (AW).

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SiR"3 Si R"3
0 0
Ri Ri -7-
R3,y(7 R3
Hal
R4 + 0 0 R4
Y---,R6 Y R6
R5 H R2 H R2 R5
formula (AU) formula (AW) formula (AVV) formula
(AAC)
base, solvent
" SiR"3 SiR",
// base, solvent
Ri R1
0 0
R3 0
R
-- R2 oxidant R3 2
-.- .
R4 H R4 H
Y
Re solvent
Y R6
R5 R5
formula (AV)
formula (AAD)
1
protic acid or
Lewis acid
S
/
/
,F1,0 R1 iR"3
R'
R4 .'==
Y R2
0
R5 R5
formula (P)
Similarly, a compound of formula (L) can also be prepared from a compound of
formula
(RAE). A compound of formula (AY) is known in the literature or can be
prepared from known
reagents using known methods.

CA 02892076 2015-05-20
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PCT/EP2013/077541
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o o
R4 )ç") + o Ri Hal
0 Ri Hal
RR4 3 Hal
Y-----.R6 Y R6
R5 H R2 H R2 R5
formula (AU) formula (AY) formula (AY)
formula (AAC)
base, solvent
i
Hal Hal base, solvent
0
R1 R1
0
R3 -- R2 oxidant R R3 0 2
_,.. ....¨
R4 R5 H
Y solvent R4 H
R6 Y R6
R5
formula (AX)
formula (AAE)
1
protic acid or
Lewis acid
H, Ri Hal
0
R3
R4 -.-
Y R2
0
R5 R6
formula (L)
Similarly, a compound of formula (W) can also be prepared from a compound of
formula
(AAF), which can be prepared using similar chemistry to that described
previously.

CA 02892076 2015-05-20
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o o
R
R1 401 R1 õI
R3) r11
) N Hal
R4=3\)1) + 0 o +R4\
Y----... Y __ ---
R6 R6
R5 H R2 H R2 R5
formula (AU) formula (AAA) formula (AAA)
formula (AAC)
base, solvent
i
base, solvent
0
Ri Ri
0
R3 -- R2 oxidant R3 o
R2
R4 R6 H -.- ...,
Y R4 R5 R6 solvent H
Y
R5
formula (AZ)
formula (AAF)
1
protic acid or
Lewis acid
H,0 Ri
R3
R4
Y R2
0
R5 R6
formula (W)
In a further approach, a compound of formula (A), wherein X is methyl, may be
prepared by
reacting a compound of formula (AAH) with a with an aryllead tricarboxylate,
in the presence
of a suitable ligand and in a suitable solvent. Similar reactions are
described in the literature
(see for example M. Muehlebach etal., W008/071405; J. Pinhey, B. Rowe, Aust.
J. Chem.,
(1979), 32, 1561-6; J. Morgan, J. Pinhey, J. Chem. Soc. Perkin Trans. 1,
(1990), 3, 715-20).
Preferably the aryllead tricarboxylate is an aryllead triacetate of formula
(AAG). Preferably
the ligand is a nitrogen containing heterocycle such as N,N-
dimethylaminopyridine, 1,10-
phenanthroline pyridine, bipyridine, or imidazole, and one to ten equivalents
of ligand with
respect to a compound of formula (AAG) is preferably used. Most preferably the
ligand is
N,N-dimethylaminopyridine. The solvent is preferably chloroform,
dichloromethane or

CA 02892076 2015-05-20
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toluene, most preferably chloroform, or a mixture of chloroform and toluene.
Preferably the
reaction is conducted at a temperature of -10 C to 100 C, most preferably at
40-90 C).
3 0 R
R4
Ri
ligand, solvent 4 R3 0
AcO,
-100C to 1000C
Ac0 I 2 R2
R5 R OAc R 0
R5 R6
formula (AAH) formula (AAG) formula (A)
Compounds of formula (AAH), wherein Y is 0, are known compounds or may be
prepared by
routes analogous to those described in the literature (see, for example, M.
Muehlebach etal.,
W008/071405; M. Morgan and E. Heyningen, J. Am. Chem Soc., (1957), 79, 422-
424; I.
Korobitsyna and K. Pivnitskii, Russian Journal of General Chemistry, (1960),
30, 4016-4023;
T. Terasawa, and T. Okada, J. Org. Chem., (1977), 42(7), 1163-1169; R.
Anderson etal.
US5089046; R. Altenbach, K. Agrios, I. Drizin and W. Carroll, Synth. Commun.,
(2004), 34
(4) 557-565; R. Beaudegnies etal., W02005/123667; W. Li, G. Wayne, J.
Lallaman, S.
Chang, and S. Wittenberger, J. Org. Chem. (2006), 71, 1725-1727; R. Altenbach,
M. Brune,
S. Buckner, M. Coghlan, A. Daza, A. Fabiyi, M. Gopalakrishnan, R. Henry, A.
Khilevich, M.
Kort, I. Milicic, V. Scott, J. Smith, K. Whiteaker, and W. Carroll, J. Med.
Chem, (2006),
49(23), 6869-6887; Carroll et al., WO 2001/083484 Al; J. K. Crandall, W. W.
Conover, J.
Org. Chem. (1978), 43(18), 3533-5; I. K. Korobitsyna, 0. P. Studzinskii,
Chemistry of
Heterocyclic Compounds (1966), (6), 848-854).
Compounds of formula (AAH), wherein Y is S, are known compounds or may be
prepared by
routes analogous to those described in the literature (see, for example, E.
Fehnel and A.
Paul, J. Am. Chem Soc., (1955), 77, 4241-4244; E. Er and P. Margaretha,
Helvetica Chimica
Acta (1992), 75(7), 2265-69; H. Gayer etal., DE 3318648 Al).
Compounds of formula (AAH), wherein Y is C(0), are known compounds or may be
prepared
by routes analogous to those described in the literature (see, for example, R.
GOtz and N.
Gotz, W02001/060776 R. GOtz etal. WO 2000/075095; M. Benbakkar etal., Synth.
Commun. (1989) 19(18) 3241-3247; A. Jain and T. Seshadri, Proc. Indian Acad.
Sci. Sect. A,
(1955), 42, 279); N. Ahmad etal., J. Org. Chem., (2007), 72(13), 4803-4815);
F. Effenberger
etal., Chem. Ber., (1986), 119, 3394-3404 and references therein).

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Compounds of formula (AAH), wherein Y is CR8R9 are known compounds of may be
prepared by routes analogous to those described in the literature (see for
example, M.
Muehlebach etal., W008/110307; M. Muehlebach at al., W008/110308; S. Spessard
and B.
Stoltz, Organic Letters, (2002), Vol. 4, No. 11, 1943-1946; F. Effenberger
etal., Chem. Ber.,
(1984), 117, 3280-3296; W. Childers etal., Tetrahedron Lett., (2006), 2217-
2218; W.
Childers etal., US2006/0004108; H. Schneider and C. Luethy, EP1352890; D.
Jackson, A.
Edmunds, M. Bowden and B. Brockbank, W02005/105745 and W02005/105717; R.
Beaudegnies, C. Luethy, A. Edmunds, J. Schaetzer and S. Wendeborn,
W02005/123667; J-
C. Beloeil, J-Y. Lallemand, T. Prange, Tetrahedron, (1986), Vol. 42. No. 13,
3491-3502; G.
Stork and R. Danheiser, J. Org. Chem., (1973), 38(9), 1775-1776; H. Favre
etal., Can. J.
Chem. (1956), 34 1329-39; R. Shriner and H. Todd, Org. Synth. Coll. Vol. II,
(1943), 200-
202).
A compound of formula (AAI), wherein X is methyl, may be prepared from a
compound of
formula (AAJ) by treatment with lead tetraacetate in a suitable solvent (for
example
chloroform) at 25 C to 100 C (preferably 25-50 C), and optionally in the
presence of a
catalyst such as mercury diacetate, according to procedures described in the
literature (for
example see, K. Shimi, G. Boyer, J-P. Finet and J-P. Galy, Letters in Organic
Chemistry,
(2005), 2, 407-409; J. Morgan and J. Pinhey, J. Chem. Soc. Perkin Trans. 1;
(1990), 3,
715-720).
R1 Pb(0A04 Ri
HO, AcO,
solvent, catalyst, ,Pb
I 2
OH R 25 C to 100 C Ac0 I
OAc R2
formula (AAJ) formula (AAI)
An aryl boronic acid of formula (AAJ), wherein X is methyl, may be prepared
from an aryl
halide of formula (AE), wherein Hal is bromine or iodine by known methods
(see, for
example, W. Thompson and J. Gaudino, J. Org. Chem, (1984), 49, 5237-5243 and
R.
Hawkins etal., J. Am. Chem. Soc., (1960), 82, 3053-3059). Thus an aryl halide
of formula
(AE) may be treated with an alkyl lithium or alkyl magnesium halide at low
temperature, and
the aryl magnesium or aryl lithium reagent obtained is allowed to react with a
trialkyl borate,
B(OR")3, preferably trimethylborate, to give an aryl dialkylboronate which may
be hydrolysed
to the desired boronic acid of formula (AAJ), where X is methyl, under acidic
conditions.
Alternatively the same overall transformation of compound (AE) to compound
(AAJ), wherein

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X is methyl, may be achieved through a palladium-catalysed borylation reaction
under known
conditions using known reagents (see for example T. Ishiyama, M. Murata, N.
Miyaura, J.
Org. Chem. (1995), 60, 7508-7501; and K. L. Billingsley, T. E. Barder, S. L.
Buchwald,
Angew. Chem. Int. Ed. (2007), 46, 5359-5363), followed by hydrolysis of the
intermediate
boronate ester.
R1 R1
1. Alkyl lithium or Grignard
HO,
Hal 2. B(OR')3
R2 OH R2
3. H30+
formula (AE) formula (AAJ)
Pd-catalysed
borylation
hydrolysis
X
R1
RO,
OR R2
In an alternative approach, a compound of formula (A), wherein X is methyl,
may be
prepared by the reaction of a compound of formula (AAK), wherein Ar is an aryl
moiety
(preferably phenyl) with an arylboronic acid of formula (AAJ), wherein X is
methyl, in the
presence of a suitable palladium catalyst, a suitable base, an optionally in
the presence of a
suitable ligand or additive, and in a suitable solvent.
3 0 o Ri
Ri
R4I¨Ar
HO catalyst, ligand 4
R
13
0 base, solvent R2
R5 R6 OH R2 0
R5 R6
formula (AAK) formula (AAJ) formula (A)
Suitable palladium catalysts include, for example palladium(II) dihalides,
palladium(II) acetate
and palladium(II) sulfate, and is preferably palladium(II) acetate. Suitable
ligands include
triphenylphosphine, tricyclopentylphosphine, tricyclohexylphosphine, 2-dicyclo-
hexylphosphino-2',6'-dimethoxybiphenyl, 2-dicyclohexylphosphino-2',4',6'-
triisopropyl-
biphenyl, 1,1'-bis(diphenylphosphino)ferrocene and 1,2-
bis(diphenylphosphino)ethane. The

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reaction may also be carried out in the presence of other additives, such as
tetralkylammonium salts, for example, tetrabutylammonium bromide. Suitable
bases include
alkali metal hydroxides, especially lithium hydroxide. A suitable solvent is
aqueous 1,2-
dimethoxyethane.
A compound of formula (AAK), wherein Ar is phenyl, may be prepared from a
compound of
formula (AAH) by treatment with a hypervalent iodine reagent such as a
(diacetoxy)iodobenzene or iodosylbenzene and a base such as aqueous sodium
carbonate,
lithium hydroxide or sodium hydroxide in a solvent such as water or an aqueous
alcohol such
as aqueous ethanol according to the procedures of K. Schank and C. Lick,
Synthesis (1983),
392; R. Moriarty eta!, J. Am. Chem. Soc, (1985), 107, 1375, or of Z. Yang
etal., Org. Lett.,
(2002), 4 (19), 3333:
R311 RI
R4
Ph1(0A02 R4
Ph
base, solvent
0
R6 R6 R6 R6
formula (AAH) formula (AAK)
wherein Ar is phenyl
In a further approach, a compound of formula I, wherein X is methyl, may be
prepared by
reacting a compound of formula (AAL) (wherein G is preferably Ci_zi alkyl, and
Hal is a
halogen, preferably bromine or iodine), with an arylboronic acid of formula
(AAJ) in the
presence of a suitable palladium catalyst (for example 0.001-50% palladium(II)
acetate with
respect to compound (AAL)) and a base (for example 1 to 10 equivalents
potassium
phosphate with respect to compound (AAL)) and preferably in the presence of a
suitable
ligand (for example 0.001-50% (2-dicyclohexylphosphino)-2',6'-
dimethoxybiphenyl with
respect to compound (AAL)), and in a suitable solvent (for example toluene),
preferably
between 25 C and 200 C. Similar couplings are known in the literature (see for
example, Y.
Song, B. Kim and J.-N. Heo, Tetrahedron Letters (2005), 46 (36), 5987-5990). A
compound
of formula I, wherein X is preferably methyl, can be converted to a compound
of formula (A)
by hydrolysis of the enol ether under known conditions.

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G,0
R
G,OR1
R \....).Hal R3
R4 catalyst, ligand
+ HO,B R4
base, solvent
0
01H R2 R2
0
R5 R6
R5 R6
formula (AAL) formula (AAJ) formula I
hydrolysis
X
o Ri
R3
R4
R2
0
R5 R6
formula A
A compound of formula (AAL) may be prepared by halogenating a compound of
formula
(AAH), followed by reaction of the resulting halide of formula (AAN) with a 01-
04 alkyl halide
or tri-01_04-alkylorthoformate under known conditions, for example by the
procedures of R.
Shepherd and A. White (J. Chem. Soc. Perkin Trans. 1 (1987), 2153-2155) and Y.-
L. Lin et
a/. (Bioorg. Med. Chem. (2002), 10, 685-690). Alternatively, a compound of
formula (AAL)
may be prepared by reacting a compound of formula (AAH) with a 01.C4 alkyl
halide or a tri-
C1_04-alkylorthoformate, and halogenating the resulting enol ether of formula
(RAM) under
known conditions (see for example Y. Song, B. Kim and J.-N. Heo, Tetrahedron
Letters
(2005), 46(36), 5987-5990).

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o
Hal
halogenation
YO
R5 R6 alkylation
formula (PAN) G,
3 0
3 0
).y
R42Hal
R4
0
R5
0 R6
R5 R6
formula (AAL)
formula (AAH)
G,
R
alkylation
R4Lhalogenation
R5 R6
formula (PAM)
In a further approach, a compound of formula (A), wherein X is methyl, may be
prepared by
reacting a compound of formula (AAH) with a compound of formula (AE) in the
presence of a
5 suitable palladium catalyst (for example 0.001-50% palladium(II) acetate
with respect to
compound (AAH)) and a base (for example Ito 10 equivalents potassium phosphate
with
respect to compound (AAH)) and preferably in the presence of a suitable ligand
(for example
0.001-50% (2-dicyclohexylphosphino)-2',4',6'-triisopropylbiphenyl with respect
to cornpound
(AAH)), and in a suitable solvent (for example dioxane), preferably between 25
C and 200 C
10 and optionally under microwave heating.
3 0 X Ri
2)L.
Ri 3 0
R4
catalyst, ligand
R4
Hal base, solvent R2
R5 R6 R2 0
R5 R6
formula (AAH) formula (AE) formula (A)
Similar couplings are known in the literature (see for example, S. Buchwald et
al., J. Am.
15 Chem. Soc. (2000), 122, 1360-1370; B. Hong etal. WO 2005/000233).
Alternatively, a
compound of formula (A) may be prepared by reacting a compound of formula
(AAH) with a

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compound of formula (AE) in the presence of a suitable copper catalyst (for
example 0.001-
50% copper(I) iodide with respect to compound (AAH)) and a base (for example 1
to 10
equivalents cesium carbonate with respect to compound (AAH)) and preferably in
the
presence of a suitable ligand (for example 0.001-50% L-proline with respect to
compound
(AAH)), and in a suitable solvent (for example dimethylsulfoxide), preferably
between 25 C
and 200 C. Similar couplings are known in the literature (see for example, Y.
Jiang et al.,
Synlett, (2005), 18, 2731-2734, and X. Xie etal., Organic Letters (2005),
7(21), 4693-4695).
A compound of formula (P), wherein R" is Cratalkyl, can also be prepared using
using
similar methods described previously, starting from silylated precursors
(AAO), (AAP) and
(AAI). Compounds (AAO), (AAP) and (AA!) are known compounds, or can be
prepared using
similar methods to those described previously.

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G,
/
, 0
R1 /
R-
Hal
R4 .õ
4" HO,
Y B
0 I
OH R2
R5 R6
formula (AAP)
formula (AAL)
icatalyst, ligand
base, solvent
SiR"3
, G,0 R1
R'
R4
Y R2
0
R5 R6
30 30
R). R
I¨Ar
4.2. R1 R4 /
hydrolysis
Y Y
6 0 SiR"3 0
R5 R R5 R6
3 0
formula (AAH) R formula (AAK)
ligand, solvent 4 catalyst, ligand
__________________________ . R < _____
+ -10 C to 100 C Y R2 base, solvent -- +
SiR"3 0 SiR"3
R5 R6 Ri
AcO, formula (P) HO,
B
,PID
I
Ac0 I OH R2
OAc R2
catalyst, ligand
base, solvent formula (AAP)
formula (AAO)
SiR"3
2,k. Ri ./-..,
R4 +
Y)(".o Hal
R5 R6 R2
formula (AAH) formula (Al)
Similiarly, a compound of formula (L) can also be prepared from suitable
halogenated
precursors, using similar methods to those described previously.
5

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G,0
R1
Hal
J.R3
Hal
+ HO,
Y -B
0 I
R2
R5 R6 OH
formula (AAR)
formula (AAL)
catalyst, ligand
,I
base, solvent
G, R1
Hal
0
R3
R4 \,
Y R2
o
R 5 R6
3 0
R4_R''..
hydrolysis R4 I¨Ar
YO Y
5/
R \ R6 'e-'0
R1 R5r\R6
Hal
formula (AAH)
3 0
R formula (AAK)
ligand, solvent 4 catalyst, ligand
+ ________________________ . R
-10 C to 100 C Y R2 base, solvent +
o
R1 daNi Hal
R5 R6
IIIP
R1
AcO, diki Hal
Pb formula (L) HO.õ 11,
Ac0 I B
OAc R2
i
OH R2
formula (AAQ) catalyst, ligand
base, solvent formula (AAR)
R311:il
R
R4------"--.' 1 Hal" +
Yc) Hal
I \6
R R R2
formula (AAH) formula (AN)
Similarly, a compound of formula (W) can also be prepared from suitable
precursors, using
similar methods to those described previously.
5

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Ri 401
R3
R4 Hal
13 HO,
Y B
0 I
OH R2
R5 R6
formula (AAT)
formula (AAL)
Icatalyst, ligand
base, solvent
G,0 Ri
R3
R4
Y R2
0
R5 R6
3 0
R4 R3
hydrolysis R4 /I¨Ar
R5 R o
, o R1 R5 R6
formula (H)
ligand, solvent R catalyst, ligand formula (AAK)
________________________ ... R4 .g _____
-100C to 100 C Y 6 R2 base, solvent +
R1 i R
si 0
R R1 401
AcO,
,Pb
Ac0 I formula (W) HO.,
OAc R2 B
I
OH R2
formula (AAS) catalyst, ligand
base, solvent formula (AAT)
R1 0
R4 +
Y
0 Hal
R5 R6 R2
formula (AAF) formula (AR)
Furthermore, a compound of formula (L) can be prepared by reacting a compound
of formula
5 (AAH) with a halonitrobenzene of formula (AA)() (under conditions similar
to those described
for coupling a compound of formula (RAH) and a compound of formula (RE) to
produce a
compound of formula (A)), to produce a compound of formula (AAW) which is then
reduced
under standard conditions (for a similar example see T. N. Wheeler,
CA1113959). The
aniline (AAV) is then converted to the aryl halide (L) under Sandmeyer
conditions (for a

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similar example see T. N. Wheeler, CA1113959). Alternatively, a compound of
formula AAU,
wherein X is chlorine, can be prepared by reacting the aniline of formula AAV
with 1,1-
dichloroethylene, a suitable metal salt such as copper(II) chloride, a
suitable metal or alkyl
nitrite in a suitable solvent at a suitable temperature. Such a reaction is an
example of a
Meerwein arylation, and examples are known in the literature (see for example
T. Himmler,
US 20100234651 and J-P. A. M. Bongartz, J. T. M. Linders, L. Meerpoel, G. S.
E. Van
Lommen, E. Coesemans, M. Braeken, C. F. R. N. Buyck, M. J. M. Berwaer, K. A.
G. J. M. De
Waepenaert, P. W. M. Roevens, G. M. Boeckx, P. V. Davidenko, WO 2008148868).
A compound of formula (A) can be prepared from a compound of formula (AAU)
under
similar conditions to those described to convert a compound of formula (J) to
a compound of
formula (D).
Hal
3 0 Ri
R4
R2
0
R5 R6
formula (L)
R3
R4 Sandmeyer
0
R5 R6
NO2 NH2
3 0 Ri
3 0 Ri
formula (AAH) cata base, lyst, ligand
solvent 4 Reduction
R2 R2
0 0
Ri NO2 R5 R6 R5 R6
formula (AAW)
Hal formula (AAV)
R2
formula (AAX) Meerwein
X
o Ri Ri X
R3 0
X
R4
R4 X
R2 R2
0 0
R5 R6 R5 R6
formula (A) formula (AAU)

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Processes for preparation of 4-ethynyl-phenyl or 4-(but-1-ynyI)-phenyl cyclic
dione
compounds within formula (ZZ)
4-Ethynyl-phenyl cyclic dione compounds (and keto-enol derivatives thereof),
within formula
(ZZ) as disclosed herein in which XX is hydrogen, can be prepared following
the procedures
described herein, e.g. hereinabove, by substituting, in the relevant cases,
the appropriate
acetylene-based reagents in the relevant reaction(s), particularly with
reference to literature
precedence, or by deprotection of silyl (SiR"3) substituted acetylene
compounds (such as a
compound of formula (P), (Al), (AW), (AAP), (RAO), provided that in this case
these have a
narrowly defined cyclic dione (or cyclic keto-enol derivative thereof)
according tot
corresponding to the cyclic dione or cyclic keto-enol as defined in in formula
(ZZ)), e.g. using
known conditions. See for example Examples 17, 18 and 19 hereinafter.
In one embodiment, 4-(but-1-ynyI)-phenyl cyclic dione compounds (and keto-enol
derivatives
thereof), within formula (ZZ) as disclosed herein in which XX is ethyl, are
prepared using an
appropriate modification of the processes to prepare the 4-(prop-1-ynyI)-
phenyl cyclic dione
compounds within formula (I).
Herbicidal compositions
In another aspect, the present invention provides a herbicidal composition,
e.g. for use in a
method of controlling weeds (e.g. monocotyledonous such as grassy weeds) in
crops of
useful plants, which composition comprises a compound of formula (I) as
defined herein (e.g.
a herbicidally effective amount thereof), and a substantially-inert
agrochemically acceptable
substance (e.g. an agrochemically acceptable carrier, diluent and/or solvent,
an
agrochemically acceptable adjuvant, an an agrochemically acceptable emulsifier
/ surfactant
/ surface-active substance, and/or another agrochemically acceptable
additive).
In a further aspect, the present invention provides a herbicidal composition,
e.g. for use in a
method of controlling weeds (e.g. monocotyledonous such as grassy weeds) in
crops of
useful plants, comprising a compound of formula (I) as defined herein (e.g. a
herbicidally
effective amount thereof), and an agrochemically acceptable carrier, diluent
and/or solvent.

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In all aspects of the invention, the compound of the formula (I) is optionally
present (e.g.
where chemically possible) as an agrochemically acceptable salt thereof.
The compounds of formula (I) according to the invention can be used as crop
protection
agents in unmodified form, as obtained by synthesis, but, for use as
herbicides, they are
generally formulated into herbicidal compositions (formulations), e.g. in a
variety of ways,
containing one or more substantially-inert agrochemically acceptable
substances (e.g. an
agrochemically acceptable carrier, diluent and/or solvent, an agrochemically
acceptable
adjuvant, an an agrochemically acceptable emulsifier/ surfactant / surface-
active substance,
and/or another agrochemically acceptable additive).
The formulations (herbicidal compositions) can be in various physical forms,
for example in
the form of dusting powders, gels, wettable powders, coated or impregnated
granules for
manual or mechanical distribution on target sites, water-dispersible granules,
water-soluble
.. granules, emulsifiable granules, water-dispersible tablets, effervescent
compressed tablets,
water-soluble tapes, emulsifiable concentrates, microemulsifiable
concentrates, oil-in-water
(EW) or water-in-oil (WO) emulsions, other multiphase systems such as
oil/water/oil and
water/oil/water products, oil flowables, aqueous dispersions, oily
dispersions,
suspoemulsions, capsule suspensions, soluble liquids, water-soluble
concentrates (with
water or a water-miscible organic solvent as carrier), impregnated polymer
films or in other
forms known, for example, from the Manual on Development and Use of FAO
Specifications
for Plant Protection Products, 5th Edition, 1999. The active ingredient may be
incorporated
into microfibers or micro-rods formed of polymers or polymerizable monomers
and having
diameter of about 0.1 to about 50 microns and aspect ratio of between about 10
and about
1000.
Such formulations can either be used directly or are diluted prior to use.
They can then be
applied through suitable ground or aerial application spray equipment or other
ground
application equipment such as central pivot irrigation systems or drip/trickle
irrigation means.
.. Diluted formulations can be prepared, for example, with water, liquid
fertilisers, micro-
nutrients, biological organisms, oil or solvents.
The formulations can be prepared, for example, by mixing the active ingredient
with formula-
tion adjuvants in order to obtain compositions in the form of finely divided
solids, granules,

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solutions, dispersions or emulsions. The active ingredients can also be
contained in fine
microcapsules consisting of a core and a polymeric shell. Microcapsules
usually have a
diameter of from 0.1 to 500 microns. They contain active ingredients in an
amount of about
from 25 to 95 c)/0 by weight of the capsule weight. The active ingredients can
be present in the
form of liquid technical material, in the form of a suitable solution, in the
form of fine particles
in solid or liquid dispersion or as a monolithic solid. The encapsulating
membranes comprise,
for example, natural and synthetic gums, cellulose, styrene-butadiene
copolymers or other
similar suitable membrane forming material, polyacrylonitrile, polyacrylate,
polyester,
polyamides, polyureas, polyurethane, aminoplast resins or chemically modified
starch or
other polymers that are known to the person skilled in the art in this
connection.
Alternatively it is possible for fine so called "microcapsules" to be formed
wherein the active
ingredient is present in the form of finely divided particles in a solid
matrix of a base
substance, but in that case the microcapsule is not encapsulated with a
diffusion limiting
membrane as outlined in the preceding paragraph.
The active ingredients may be adsorbed on a porous carrier. This may enable
the active
ingredients to be released into their surroundings in controlled amounts (e.g.
slow release).
Other forms of controlled release formulations are granules or powders in
which the active
ingredient is dispersed or dissolved in a solid matrix consisting of a
polymer, a wax or a
suitable solid substance of lower molecular weight. Suitable polymers are
polyvinyl acetates,
polystyrenes, polyolefins, polyvinyl alcohols, polyvinyl pyrrolidones,
alkylated polyvinyl
pyrrolidones, copolymers of polyvinyl pyrrolidones and maleic anhydride and
esters and half-
esters thereof, chemically modified cellulose esters like carboxymethyl
cellulose, methyl
cellulose, hydroxyethyl cellulose, examples of suitable waxes are polyethylene
wax, oxidized
polyethylene wax, ester waxes like montan waxes, waxes of natural origin like
carnauba wax,
candelilla wax, bees wax etc. Other suitable matrix materials for slow release
formulations
are starch, stearin, lignin.
The formulation ingredients (e.g. inert ingredients) suitable for the
preparation of the
compositions according to the invention are generally known per se.
As a liquid carrier and/or solvent (e.g. organic solvent), e.g. for use in the
herbicidal
composition(s) according to the invention, there may be used: water, an
aromatic solvent

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such as toluene, m-xylene, o-xylene, p-xylene or a mixture thereof, cumene, an
aromatic
hydrocarbon blend with a boiling range between 140 and 320 C (e.g. known
under various
trademarks such as Solvesso , Shellsol A , Caromax , Hydroson, a paraffinic or
isoparaffinic carrier such as paraffin oil, mineral oil, a de-aromatized
hydrocarbon solvent
with a boiling range between 50 and 320 C (e.g. known for instance under the
trademark
Exxson, a non-dearomatized hydrocarbon solvent with a boiling range between
100 and
320 C (e.g. known under the tradename Varsol ), an isoparaffinic solvent with
a boiling
range between 100 and 320 C (e.g. known known under tradenames like Isopar
or Shellsol
T ), a hydrocarbon such as cyclohexane, tetrahydronaphthalene (tetralin),
decahydronaphthalene, alpha-pinene, d-limonene, hexadecane, isooctane; an
ester solvent
such as ethyl acetate, n- or iso- butyl acetate, amyl acetate, i-bornyl
acetate, 2-ethylhexyl
acetate, a 06 ¨ 018 alkyl ester of acetic acid (e.g. known under the tradename
Exxate ), lactic
acid ethylester, lactic acid propylester, lactic acid butylester, benzyl
benzoate, benzyl lactate,
dipropyleneglycol dibenzoate, or a dialkyl ester of succinic, maleic or
fumaric acid; a polar
solvent such as N-methyl pyrrolidone, N-ethyl pyrrolidone, 03-018-alkyl
pyrrolidones, gamma-
butyrolactone, dimethylsulfoxide, N,N-dimethylformamide, N,N-
dimethylacetamide, N,N-
dimethyllactamide, a 04-018 fatty acid dimethylamide, benzoic acid
dimethylamide,
acetonitrile, acetone, methyl ethyl ketone, methyl-isobutyl ketone, isoamyl
ketone, 2-
heptanone, cyclohexanone, isophorone, methyl isobutenyl ketone (mesityl
oxide),
acetophenone, ethylene carbonate, propylene carbonate, or butylene carbonate;
an alcoholic solvent or diluent such as methanol, ethanol, propanol, n- or iso-
butanol, n- or
iso- pentanol, 2-ethyl hexanol, n-octanol, tetrahydrofurfuryl alcohol, 2-
methy1-2,4-
pentanediol, 4-hydroxy-4-methy1-2-pentanone, cyclohexanol, benzyl alcohol,
ethylene glycol,
ethylene glycol butyl ether, ethylene glycol methyl ether, diethylene glycol,
diethylene glycol
butyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl
ether,
propylene glycol, dipropylene glycol, dipropylene glycol monomethyl ether, or
another similar
glycol monoether solvent based on a ethylene glycol, propylene glycol or
butylene glycol
feedstock, triethylene glycol, polyethylene glycol (e.g. PEG 400), a
polypropylenglycol with a
molecular mass of 400 - 4000, or glycerol;
glycerol acetate, glycerol diacetate, glycerol triacetate, 1,4-dioxane,
diethylene glycol
abietate, chlorobenzene, chlorotoluene; a fatty acid ester such as methyl
octanoate,
isopropyl myristate, methyl laurate, methyl oleate, a mixture of 08-C10 fatty
acid methyl
esters, rapeseed oil methyl ester, rapeseed oil ethyl ester, soybean oil
methyl ester, soybean
oil ethyl ester; a vegetable oil (e.g. rapeseed oil or soybean oil); a fatty
acid such as oleic

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acid, linoleic acid, or linolenic acid; or an ester of phosphoric or
phosphonic acid such as
triethyl phosphate, a C3-018-tris-alkyl phosphate, an alkylaryl phosphate, or
bis-octyl-octyl
phosphonate.
Water is generally the liquid carrier of choice for the dilution of the
concentrates.
Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite
clay, silica (fumed
or precipated silica and optionally functionalised or treated, for instance
silanised), attapulgite
clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium
montomorillonite,
cottonseed husks, wheatmeal, soybean flour, pumice, wood flour, ground walnut
shells,
lignin and similar materials, as described, for example, in the EPA CFR
180.1001. (c) & (d).
Powdered or granulated fertilisers can also be used as solid carriers.
A large number of surface-active substances can advantageously be used both in
solid and
.. in liquid formulations (herbicidal compositions), especially in those
formulations (herbicidal
compositions) which can be diluted with a carrier prior to use. Surface-active
substances
may be anionic, cationic, amphoteric, non-ionic or polymeric and they may be
used as
emulsifiying, wetting, dispersing or suspending agents or for other purposes.
Typical surface-
active substances include, for example, salts of alkyl sulfates, such as
diethanolammonium
.. lauryl sulfate; Sodium lauryl sulfate, salts of alkylarylsulfonates, such
as calcium or sodium
dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as
nonylphenol
ethoxylates; alcohol-alkylene oxide addition products, such as tridecyl
alcohol ethoxylate;
soaps, such as sodium stearate; salts of alkylnaphthalenesulfonates, such as
sodium
dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as
sodium di(2-
ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate;
quaternary amines, such
as lauryl trimethylammonium chloride, polyethylene glycol esters of fatty
acids, such as
polyethylene glycol stearate; block copolymers of ethylene oxide and propylene
oxide; and
salts of mono- and di-alkyl phosphate esters; and also further substances
described e.g. in
"McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp.,
Ridgewood, New
Jersey, 1981.
Further formulation ingredients (e.g. inert ingredients) which can typically
be used in
formulations (herbicidal compositions) include crystallisation inhibitors,
viscosity-modifying
substances, suspending agents, dyes, anti-oxidants, foaming agents, light
absorbers, mixing

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aids, anti-foams, complexing agents, neutralising or pH-modifying substances
and/or buffers,
corrosion-inhibitors, fragrances, wetting agents, absorption improvers,
micronutrients,
plasticisers, glidants, lubricants, dispersants, thickeners, anti-freezes,
microbiocides,
compatibility agents and/or solubilisers; and/or also liquid and solid
fertilisers.
The compositions (formulations) may also comprise additional active
substances, for
example further herbicides, herbicide safeners, plant growth regulators,
fungicides or
insecticides.
The compositions according to the invention can additionally include an
additive (commonly
referred to as an adjuvant), comprising a mineral oil, an oil of vegetable or
animal origin,
alkyl (e.g. 01-C6alkyl) esters of such oils, or mixtures of such oils and oil
derivatives / oil
esters. The amount of oil additive (oil adjuvant) used in the composition
according to the
invention is generally from 0.01 to 10 %, based on the spray mixture. For
example, the oil
additive (oil adjuvant) can be added to the spray tank in the desired
concentration after the
spray mixture has been prepared. Preferred oil additives (oil adjuvants)
comprise mineral oils
or an oil of vegetable origin, for example rapeseed oil, olive oil or
sunflower oil, emulsifiable
vegetable oil, such as AMIGO (Loveland Products Inc.), 01-C6alkyl esters of
oils of
vegetable origin, for example the methyl esters, or an oil of animal origin,
such as fish oil or
beef tallow. A preferred oil additive (oil adjuvant) contains methylated
rapeseed oil
(rapeseed oil methyl ester). Another preferred oil additive (oil adjuvant)
contains, for
example, as active components essentially 80 % by weight alkyl esters of fish
oils and 15 %
by weight methylated rapeseed oil (rapeseed oil methyl ester), and also 5 % by
weight of
customary emulsifiers and pH modifiers. Especially preferred oil additives
(oil adjuvants)
comprise C1-C6alkyl ester(s) of C8-C22 fatty acid(s), especially the methyl
ester(s) of C8-C22
(especially C12-C18) fatty acid(s); preferably the methyl ester of lauric
acid, of palmitic acid, or
of oleic acid. Those esters are known as methyl laurate (CAS-111-82-0), methyl
palmitate
(CAS-112-39-0) and methyl oleate (CAS-112-62-9) respectively. A preferred
fatty acid
methyl ester derivative is AGNIQUE ME 18 RD-F0 (e.g. available from Cognis).
Those and
other oil derivatives are also known from the Compendium of Herbicide
Adjuvants, 5th
Edition, Southern Illinois University, 2000.
The application and action of the above-mentioned oil additives (oil
adjuvants) can be further
improved by combining them with surface-active substances, such as non-ionic,
anionic,

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cationic or amphoteric surfactants. Examples of suitable anionic, non-ionic,
cationic or
amphoteric surfactants, e.g. for this purpose, are listed on pages 7 and 8 of
W097/34485.
Preferred surface-active substances are anionic surfactants of the
dodecylbenzylsulfonate
type, especially the calcium salts thereof, and also non-ionic surfactants of
the fatty alcohol
ethoxylate type. As non-ionic sufactants, special preference is given to
ethoxylated 012-022
fatty alcohols preferably having a degree of ethoxylation of from 5 to 40.
Examples of
commercially available surfactants are the Genapol types (Clariant). Also
preferred are
silicone surfactants, especially polyalkyl-oxide-modified
heptamethyltrisiloxanes, which are
commercially available e.g. as SILWET L-77 , and also perfluorinated
surfactants. The
concentration of surface-active substances in relation to the total oil
additive (oil adjuvant) is
generally from 1 to 50 A by weight of the oil additive (oil adjuvant).
Examples of oil additives
(oil adjuvants) that consist of mixtures of oils and/or mineral oils and/or
derivatives thereof
with surfactants are TURBOCHARGED, ADIGOR0 (both Syngenta Crop Protection AG),
ACTIPRON (BP Oil UK Limited), AGRI-DEXCD (Helena Chemical Company).
The above-mentioned surface-active substances may also be used in the
formulations alone,
that is to say without oil additives (oil adjuvants).
Furthermore, the addition of an organic solvent to the oil additive (oil
adjuvant) / surfactant
mixture can contribute to a further enhancement of action. Suitable solvents
are, for
example, heavy aromatic hydrocarbon solvents such as SOLVESSO or AROMATIC
solvents (Exxon Corporation). The concentration of such solvents can e.g. be
from 10 to
80 `)/0 by weight of the oil additive (oil adjuvant). Such oil additives (oil
adjuvants), which may
.. be in admixture with solvents, are described, for example, in US 4 834 908.
A commercially
available oil additive disclosed therein is known by the name MERGE (BASF).
Further
such oil additives (oil adjuvants) that are preferred according to the
invention are SCORE
and ADIGOR (both Syngenta Crop Protection AG).
In addition to the oil additives (oil adjuvants) listed above, in order to
enhance the activity of
the compositions according to the invention it is also possible for
formulations of
alkylpyrrolidones, (e.g. AGRIMAX0 from ISP) to be added to the spray mixture.
Formulations
of synthetic latices, such as, for example, polyacrylamide, polyvinyl
compounds or poly-1-p-
menthene (e.g. BOND , COURIER or EMERALD ) can also be used.

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A particularly preferred oil adjuvant (oil additive), e.g. for use in the
herbicidal compositionas
of the invention, is an emulsifiable concentrate which consists of:
(i) ethoxylated alcohols, which preferably includes ethoxylated 012-022 fatty
alcohols
(preferably having a degree of ethoxylation of from 5 to 40); and
(ii) a mixture of heavy aromatic hydrocarbons, which preferably includes (or
more preferably
includes 50% or more by weight of the heavy aromatic hydrocarbons of) a
mixture of
naphthalenes each of which is substituted by one or more alkyls wherein the
alkyl(s) in total
have 1-4 carbon atoms per naphthalene molecule (e.g. Solvesso 200 ND TM); and
.. (iii) methylated rapeseed oil (rapeseed oil methyl ester) (e.g. Agnique ME
18 RD-F TM), as an
adjuvant; preferably present at about 47% w/w and/or about 45% w/v of the oil
adjuvant / oil
additive / emulsifiable concentrate. One example of such a emulsifiable
concentrate oil
adjuvant (oil additive) is ADIGOR TM, currently available in many countries
from Syngenta.
.. When the above emulsifiable concentrate oil adjuvant is used, it is
preferably added to the
herbicidal composition after dilution (e.g. with water and/or in a spray
tank), typically before
application to weeds and/or to crops of useful plants and/or to the locus
thereof. In one
particular embodiment, the herbicidal composition, e.g. after dilution (e.g.
with water and/or in
a spray tank), contains the above emulsifiable concentrate oil adjuvant, and
additionally
ammonium sulphate and/or isopropyl alcohol.
Such adjuvant oils as described in the preceding paragraphs may be employed as
a or the
carrier liquid in which an active compound is dissolved, emulsified or
dispersed as
appropriate to the physical form of the active compound.
In an alternative particular embodiment, the herbicidal composition of the
invention
comprises an agrochemically acceptable adjuvant comprising 1,2-cyclohexane
dicarboxylic
acid di-isononyl ester (e.g. CAS Registry no. 166412-78-8), e.g. as available
from BASF as
Hexamoll TM DINCH TM. "Isononyl" in this context is thought to mean one or
more, preferably
a mixture of two or more, branched isomers of 09H19. In one particular
embodiment, the
herbicidal composition, e.g. after dilution (e.g. with water and/or in a spray
tank), contains
1,2-cyclohexane dicarboxylic acid di-isononyl ester, and additionally ammonium
sulphate
and/or isopropyl alcohol.
In an alternative particular embodiment, the herbicidal composition of the
invention
comprises an agrochemically acceptable adjuvant comprising an organic
phosphate and/or

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organic phosphonate adjuvant. Preferably, the phosphate adjuvant is a tris-[04-
C12alkyl or
2-(02-C6alkoxy)ethyl-] ester of phosphoric acid, or more preferably is tris-(2-
ethylhexyl)
phosphate, tris-n-octyl phosphate and/or tris-[2-(n-butoxy)ethyl] phosphate,
or most
preferably is tris-(2-ethylhexyl) phosphate. Preferably, the phosphonate
adjuvant is a bis-
(C3-C12alkyl) ester of a C3-C12alkyl-phosphonic acid, or more preferably is
bis-(2-ethylhexyl)
(2-ethylhexyl)phosphonate, bis-(2-ethylhexyl) (n-octyl)phosphonate and/or di-n-
butyl
(n-butyl)phosphonate.
The formulations (herbicidal compositions) generally contain from 0.1 to 99 %
by weight,
especially from 0.1 to 95% by weight, of a compound of formula land from Ito
99.9% by
weight of a substantially-inert agrochemically acceptable substance, which
preferably
includes a formulation adjuvant and/or from 0 to 30 % or from 0 to 25 % (e.g.
from 0.5 to
30 % or from 0.5 to 25 %) by weight of a surface-active substance. Whereas
herbicidal
.. compositions (especially commercial products) will preferably be formulated
as concentrates,
the end user will normally employ dilute formulations (compositions), e.g.
formulations
(compositions) diluted with water, in particular when applying the herbicidal
composition to
weeds and/or to crops of useful plants and/or to the locus thereof.
The rate of application of the compounds of formula I may vary within wide
limits and
depends upon the nature of the soil, the method of application (pre- or post-
emergence; seed
dressing; application to the seed furrow; no tillage application etc.), the
crop plant, the weed
or grass to be controlled, the prevailing climatic conditions, and other
factors governed by the
method of application, the time of application and the target crop. The
compounds of formula
I according to the invention are generally applied (preferably post-emergence)
at a rate of
from 1 to 2000 g/ha, preferably from 1 to 1000 g / ha and most preferably at
from 1 to 500 g /
ha or from 5 to 500 g/ha.
Preferred formulations / compositions have especially the following
representative
compositions:
(% = percent by weight of the composition):
Emulsifiable concentrates:
active ingredient: 0.3 to 95 %, preferably 0.5 to 60 % such as 1 to
40 A

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surface-active agents: 1 to 30 %, preferably 3 to 20% such as 5 to 15 %
solvents as liquid carrier: 1 to 80 %, preferably 1 to 60% such as 1 to 40
%
Dusts:
active ingredient: 0.1 to 10 %, preferably 0.1 to 5 %
solid carriers: 99.9 to 90 %, preferably 99.9 to 99 %
Suspension concentrates:
active ingredient: 1 to 75 %, preferably 3 to 50 % or 10 to 50 %
water: 98 to 24 %, preferably 95 to 30 % or 88 to 30 %
surface-active agents: 1 to 40 %, preferably 2 to 30 %
Wettable powders:
active ingredient: 0.5 to 90 A, preferably 1 to 80 %
surface-active agents: 0.5 to 20 (3/0, preferably 1 to 15 %
solid carriers: 5 to 95 %, preferably 15 to 90 %
Granules:
active ingredient: 0.1 to 30 %, preferably 0.1 to 15 %
solid carriers: 99.5 to 70 %, preferably 97 to 85 %
Waterdispersible granules:
active ingredient: 1 to 90 %, preferably 10 to 80 %
surface-active agents: 0.5 to 80 %, preferably 5 to 30 %
solid carriers: 90 to 10 %, preferably 70 to 30 %
The following Examples further illustrate, but do not limit, the invention.
Fl. Emulsifiable concentrates a) b) c) d)
active ingredient 5 % 10 % 25 % 50 "Yo
calcium dodecylbenzene-
sulfonate 6 % 8 A 6 % 8 %
castor oil polyglycol ether 4 "Yo 4 % 4 %
(36 mol of ethylene oxide)
octylphenol polyglycol ether 4 % 2 %
(7-8 mol of ethylene oxide)
NMP (N-methyl-2-pyrrolidone) - 10 % 20 %
aromatic hydrocarbon 85 % 68 % 65 % 16 %

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mixture 09-012
Emulsions of any desired concentration can be prepared from such concentrates
by dilution
with water.
F2. Solutions a) b) c) d)
active ingredient 5 cyo 10 % 50 % 90 %
1-methoxy-3-(3-methoxy-
propoxy)-propane 40 % 50 % - -
polyethylene glycol MW 400 20 % 10 %
NMP (N-methyl-2-pyrrolidone) - - 50 % 10 `)/0
aromatic hydrocarbon 35 % 30 % - -
mixture 09-012
The solutions are suitable for application undiluted or after dilution with
water.
F3. Wettable powders a) b) c) d)
active ingredient 5 % 25 % 50 % 80 `)/0
sodium lignosulfonate 4 A - 3 % -
sodium lauryl sulfate 2 % 3 % _ 4 %
sodium diisobutylnaphthalene-
sulfonate - 6 % 5 % 6 %
octylphenol polyglycol ether - 1 % 2 % -
(7-8 mol of ethylene oxide)
highly disperse silicic acid 1 % 3 % 5 % 10 %
kaolin 88 % 62 % 35 % -
The active ingredient is thoroughly mixed with the adjuvants and the mixture
is thoroughly
ground in a suitable mill, yielding wettable powders which can be diluted with
water to give
suspensions of any desired concentration.
F4. Coated granules a) b) c)
active ingredient 0.1 ')/0 5 'Yo 15 `)/0
highly dispersed silica 0.9 % 2 % 2 %
inorganic carrier 99.0 `)/0 93 % 83 `)/0
(diameter 0.1 - 1 mm)
e.g. Ca 003 or Si02

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The active ingredient is dissolved in methylene chloride, the solution is
sprayed onto the
carrier and the solvent is subsequently evaporated off in vacuo.
F5. Coated granules a) b) c)
active ingredient 0.1 % 5 % 15 %
polyethylene glycol MW 200 1.0 % 2 % 3 %
highly dispersed silica 0.9 % 1 % 2 %
inorganic carrier 98.0 % 92 % 80 %
(diameter 0.1 - 1 mm)
e.g. CaCO3 or SiO2
The finely ground active ingredient is applied uniformly, in a mixer, to the
carrier moistened
with polyethylene glycol. Non-dusty coated granules are obtained in this
manner.
F6. Extruded granules a) b) c) d)
active ingredient 0.1 % 3 % 5 % 15 %
sodium lignosulfonate 1.5 % 2 % 3 % 4 %
carboxymethylcellulose 1.4 ./0 2 % 2 % 2 %
kaolin 97.0 % 93 % 90 % 79 %
The active ingredient is mixed and ground with the adjuvants and the mixture
is moistened
with water. The resulting mixture is extruded and then dried in a stream of
air.
F7. Water-dispersible granules a) b) c) d)
active ingredient 5 % 10 % 40 c1/0 90 %
sodium lignosulfonate 20 % 20 % 15 % 7 %
dibutyl naphthalene sulfonate 5 cyo 5 % 4 % 2 %
Gum arabic 2 % 1 % 1 % 1 %
Diatomaceous earth 20 % 30 % 5 % _
Sodium sulfate - 4 % 5 % _
kaolin 48 % 30 % 30 % -
The active ingredient is mixed and ground with the adjuvants and the mixture
is moistened
with water. The resulting mixture is extruded and then dried in a stream of
air.

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F8. Dusts a) b) c)
active ingredient 0.1 % 1 `)/0 5 %
talcum 39.9 % 49 % 35 %
kaolin 60.0 % 50 % 60 %
Ready-to-use dusts are obtained by mixing the active ingredient with the
carriers and
grinding the mixture in a suitable mill.
F9. Suspension concentrates a) b) c) d)
active ingredient 3 % 10 % 25 `)/0 50 %
propylene glycol 5% 5% 5% 5%
nonylphenol polyglycol ether 1 % 2 %
(15 mol of ethylene oxide)
sodium lignosulfonate 3 cy. 3 % 7 % 6 %
heteropolysacharide (Xanthan) 0.2 % 0.2 % 0.2 % 0.2 %
1,2-benzisothiazolin-3-one 0.1 % 0.1 % 0.1 % 0.1 %
silicone oil emulsion 0.7 % 0.7 % 0.7 % 0.7 %
water 88 % 80 ./0 60 ./0 38 %
The finely ground active ingredient is intimately mixed with the adjuvants,
yielding a suspen-
sion concentrate from which suspensions of any desired concentration can be
prepared by
dilution with water.
Herbicidal uses - crops of useful plants, weeds, application rates, et al.
In a further aspect, the present invention provides a method of controlling
weeds (e.g.
monocotyledonous such as grassy weeds) in crops of useful plants, which
comprises
applying a compound of the formula (I), or a herbicidal composition comprising
such a
compound, to the weeds and/or to the plants and/or to the locus thereof.
In a further aspect, the present invention provides a herbicidal composition,
in particular for
use in a method of controlling weeds (e.g. monocotyledonous such as grassy
weeds) in
crops of useful plants, comprising a compound of formula (I) as defined herein
(e.g. a
herbicidally effective amount thereof), and an agrochemically acceptable
carrier, diluent
and/or solvent.

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In all aspects of the invention, the compound of the formula (I) is optionally
present (e.g.
where chemically possible) as an agrochemically acceptable salt thereof.
In one embodiment, the herbicidal composition also comprises one or more
further
herbicides, e.g. as mixture partner(s) for the compound of formula (I), and/or
a safener. See
the combinations and mixtures section herein for more details of examples of
these.
In all aspects of the invention (e.g. the methods of use of the invention),
crops of useful
plants, e.g. on or in which or at the locus of which the compounds or
compositions according
to the invention can be used, comprise (e.g. are), in particular: cereals
(e.g. non-oat cereals,
in particular non-oat non-sorghum non-millet cereals, more particularly wheat,
barley, rye
and/or triticale), rice, corn (maize), sugarcane, leguminous crops [preferably
soybean,
peanut, and/or pulse crops; more preferably soybean; wherein typically the
pulse crops
comprise dry beans (e.g. kidney or haricot or pinto bean which is Phaseolus
vulgaris, or
mung bean which is Vigna radiata), chickpea, blackeye bean (i.e. black-eyed
pea, Vigna
unguiculata), lentil, dry broad beans, and/or dry peas such as garden peas],
cotton, rape (in
particular oilseed rape or canola), sunflower, linseed, sugarbeet, fodder
beet, potato,
vegetables (preferably dicotyledonous vegetables), flax, tobacco, plantation
crops (such as
conifer trees, olives and/or olive trees, oil palms, coffee, or vines), and/or
fruit crops (in
particular dicotyledonous and/or broadleaved fruit, and/or in particular pome
fruit, stone fruit,
bush fruit, citrus fruit, pineapple, banana, and/or strawberry).
Preferably, in all aspects of the invention, the crops of useful plants, e.g.
on or in which or at
the locus of which the compounds or compositions according to the invention
can be used,
comprise (e.g. are): cereals (in particular non-oat cereals, more particularly
non-oat non-
sorghum non-millet cereals, even more particularly wheat, barley, rye and/or
triticale), rice,
corn (maize), sugarcane, leguminous crops [preferably soybean, peanut, and/or
pulse crops
(more preferably soybean)], cotton, rape (in particular oilseed rape or
canola), sunflower,
linseed, sugarbeet, fodder beet, potato, and/or vegetables (preferably
dicotyledonous
vegetables).
More preferably, in all aspects of the invention, the crops of useful plants,
e.g. on or in which
or at the locus of which the compounds or compositions according to the
invention can be
used, comprise (e.g. are): wheat (e.g. winter wheat, spring wheat, or durum
wheat), barley
(e.g. winter or spring barley), rye, triticale, sugarcane, leguminous crops
[preferably soybean,

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peanut, and/or pulse crops (more preferably soybean)], cotton, rape (in
particular oilseed
rape or canola), sunflower, linseed, sugarbeet, fodder beet, potato, and/or
vegetables
(preferably dicotyledonous vegetables).
Even more preferably, in all aspects of the invention, the crops of useful
plants, e.g. on or in
which or at the locus of which the compounds or compositions according to the
invention can
be used, comprise (e.g. are): leguminous crops [preferably soybean, peanut,
and/or pulse
crops; more preferably soybean; wherein typically the pulse crops comprise dry
beans (e.g.
kidney or haricot or pinto bean which is Phaseolus vulgaris, or mung bean
which is Vigna
radiata), chickpea, blackeye bean (i.e. black-eyed pea, Vigna unguiculata),
lentil, dry broad
beans, and/or dry peas such as garden peas], cotton, rape (in particular
oilseed rape or
canola), sunflower, sugarbeet, fodder beet, potato, and/or vegetables
(preferably
dicotyledonous vegetables).
The term "crops" is to be understood as also including crops that have been
rendered
tolerant to herbicides or classes of herbicides (for example ALS, GS, EPSPS,
PPO and
HPPD inhibitors, and/or 2,4-D or dicamba) as a result of conventional methods
of breeding or
genetic engineering. Examples of crops that have been rendered tolerant e.g.
to imid-
azolinones (which are ALS inhibitors), such as imazamox, by conventional
methods of
breeding include Clearfield summer rape (canola) and/or Clearfield wheat
and/or
Clearfield rice (all from BASF). Examples of crops that have been rendered
tolerant to
herbicides by genetic engineering methods include e.g. glyphosate-resistant or
glufosinate-
resistant maize or soybean varieties, in particular those commercially
available under the
trade name RoundupReady or RoundupReady 2 (both from Monsanto, both
glyphosate-
resistant) or LibertyLink (from Bayer, glufosinate-resistant). Glufosinate-
resistant rice
(LibertyLinke) also has been published.
Other crops of useful plants include 2,4-D-tolerant soybean, e.g. soybean
genetically-
modified to be tolerant to the herbicide 2,4-D, or dicamba-tolerant soybean,
e.g. soybean
genetically-modified to be tolerant to the herbicide dicamba. Such 2,4-D-
tolerant or dicamba-
tolerant soybean crops can also, in particular, be tolerant to glyphosate or
glufosinate. For
example, crops of useful plants include soybeans containing a dicamba-
tolerance trait
combined (stacked) with a glyphosate-tolerance trait, such that these soybeans
have
tolerance to the herbicides glyphosate and dicamba (for example Genuity0
Roundup
Ready 2 Xtend soybeans, currently under development by Monsanto).

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Crops are also to be understood as being those which have been rendered
resistant to
harmful insects by genetic engineering methods, for example Bt maize
(resistant to
European corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt
potatoes
(resistant to Colorado beetle). Examples of Bt maize are the Bt-176 maize
hybrids of NKO
(Syngenta Seeds). The Bt toxin is a protein that is formed naturally by
Bacillus thuringiensis
soil bacteria. Examples of toxins and transgenic plants able to synthesise
such toxins are
described in EP-A-451 878, EP-A-374 753, WO 93/07278, WO 95/34656, WO
03/052073
and EP-A-427 529. Examples of transgenic plants that contain one or more genes
which
code for an insecticidal resistance and express one or more toxins are
KnockOut (maize),
Yield Gard (maize), NuCOTIN33B0 (cotton), Bollgard (cotton), NewLeaf0
(potatoes),
NatureGarde and Protexcta0. Plant crops and their seed material can be
resistant to
herbicides and at the same time also to insect feeding ("stacked" transgenic
events). Seed
can, for example, have the ability to express an insecticidally active Cry3
protein and at the
same time be glyphosate-tolerant. The term "crops" is to be understood as also
including
crops obtained as a result of conventional methods of breeding or genetic
engineering which
contain so-called output traits (e.g. improved flavour, storage stability,
nutritional content).
In all aspects of the invention, the weeds, e.g. to be controlled and/or
growth-inhibited, may
be either monocotyledonous (e.g. grassy) and/or dicotyledonous weeds.
Preferably the
weeds, e.g. to be controlled and/or growth-inhibited, comprise or are
monocotyledonous
weeds, more preferably grassy monocotyledonous weeds.
In all aspects of the invention, typically, the monocotyledonous (preferably
grassy) weeds,
e.g. to be controlled and/or growth-inhibited, comprise (e.g. are) weeds from
the genus
Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Cyperus (a
genus of
sedges), Digitaria, Echinochloa, Eleusine, Eriochloa, Fimbristylis (a genus of
sedges),
Juncus (a genus of rushes), Leptochloa, Lolium, Monochoria, Ottochloa,
Panicum,
Pennisetum, Phalaris, Poa, Rottboellia, Sagittaria, Scirpus (a genus of
sedges), Setaria
and/or Sorghum; in particular: Alopecurus myosuroides (ALOMY, English name
"blackgrass''), Apera spica-venti, Avena fatua (AVEFA, English name "wild
oats"), Avena
ludoviciana, Avena star/is, Avena sativa (English name "oats" (volunteer)),
Brachiaria
decumbens, Brachiaria plantaginea, Bromus tectorum, Digitaria horizontalis,
Digitaria
insularis, Digitaria sanguinalis (DIGSA), Echinochloa crus-galli (English name
"common
barnyard grass", ECHCG), Echinochloa otyzoides, Echinochloa colona or colonum,
Eleusine
indica, Eriochloa villosa (English name "woolly cupgrass"), Leptochloa
chinensis, Leptochloa

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panicoides, Lolium perenne (LOLPE, English name "perennial ryegrass"), Lolium
multiflorum
(LOLMU, English name "Italian ryegrass"), Lolium persicum (English name
"Persian darnel"),
Lolium rigidum, Panicum miliaceum (English name "wild proso millet"), Phalaris
minor,
Phalaris paradoxa, Poa annua (POAAN, English name "annual bluegrass"), Scirpus
maritimus, Scirpus juncoides, Setaria viridis (SETVI, English name "green
foxtail"), Setaria
faberi (SETFA, English name "giant foxtail"), Setaria glauca, Setaria
lutescens (English name
"yellow foxtail"), Sorghum bicolor, and/or Sorghum halepense (English name
"Johnson
grass"); and/or in particular: Brachiaria platyphylla (BRAPP), Panicum
dichotomiflorum
(PAN Dl), and/or Sorghum vulgare. Alternatively or additionally, the
monocotyledonous
(preferably grassy) weeds, e.g. to be controlled and/or growth-inhibited,
comprise volunteer
corn (volunteer maize) weeds.
In one preferred embodiment of all aspects of the invention, the
monocotyledonous weeds,
e.g. to be controlled and/or growth-inhibited, are grassy monocotyledonous
weeds; in which
case they typically comprise (e.g. are) weeds from the genus Agrostis,
Alopecurus, Apera,
Avena, Brachiaria, Bromus, Cenchrus, Digitaria, Echinochloa, Eleusine,
Eriochloa,
Leptochloa, Lolium, Ottochloa, Panicum, Pennisetum, Phalaris, Poa,
Rottboellia, Setaria
and/or Sorghum. Alternatively or additionally, the monocotyledonous
(preferably grassy)
weeds, e.g. to be controlled and/or growth-inhibited, comprise volunteer corn
(volunteer
maize) weeds.
In one preferred embodiment of all aspects of the invention, the grassy
monocotyledonous
weeds, e.g. to be controlled and/or growth-inhibited, are "warm-season" (warm
climate)
grassy weeds; in which case they preferably comprise (e.g. are) weeds from the
genus
Brachiaria, Cenchrus, Digitaria, Echinochloa, Eleusine, Eriochloa, Leptochloa,
Ottochloa,
Panicum, Pennisetum, Phalaris, Rottboellia, Setaria and/or Sorghum.
Alternatively or
additionally, the grassy monocotyledonous weeds, e.g. to be controlled and/or
growth-
inhibited, comprise volunteer corn (volunteer maize) weeds. More preferably,
the grassy
monocotyledonous weeds, e.g. to be controlled and/or growth-inhibited, are
"warm-season"
(warm climate) grassy weeds comprising (e.g. being) weeds from the genus
Brachiaria,
Cenchrus, Digitaria, Echinochloa, Eleusine, Eriochloa, Panicum, Setaria and/or
Sorghum;
and/or the grassy monocotyledonous weeds, e.g. to be controlled and/or growth-
inhibited,
comprise volunteer corn (volunteer maize) weeds.

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In another particular embodiment of all aspects of the invention, the grassy
monocotyledonous weeds, e.g. to be controlled and/or growth-inhibited, are
"cool-season"
(cool climate) grassy weeds; in which case they typically comprise (e.g. are)
weeds from the
genus Agrostis, Alopecurus, Apera, Avena, Bromus, Lolium and/or Poa.
In non-oat cereal crops such as wheat and/or barley, control and/or growth
inhibition of
weeds from the genus Alopecurus, Apera, Avena, especially Avena fatua, Bromus,
Lolium,
Phalaris, and/or Setaria is preferred; in particular Alopecurus, Avena
(especially Avena
fatua), Lolium and/or Setaria (especially Setaria viridis, Setaria lutescens,
Setaria faberi
and/or Setaria glauca).
In all aspects of the invention, in a particular embodiment, the weeds, e.g.
to be controlled
and/or growth-inhibited e.g. by applying a compound of formula (I), may be
grassy
monocotyledonous weeds (e.g. Agrostis, Alopecurus, Apera, Avena, Brachiaria,
Bromus,
Cenchrus, Digitaria, Echinochloa, Eleusine, Eriochloa, Leptochloa, Lolium,
Ottochloa,
Panicum, Pennisetum, Phalaris, Poa, Rottboellia, Setaria and/or Sorghum
weeds),
- which are resistant to one or more ACCase inhibitor herbicides (ACCase =
acetyl-
coenzyme A carboxylase) selected from the group consisting of pinoxaden,
clodinafop-
propargyl, fenoxaprop-P-ethyl, diclofop-methyl, fluazifop-P-butyl, haloxyfop-P-
methyl,
quizalofop-P-ethyl, propaquizafop, cyhalofop-butyl, clethodim, sethoxydim,
cycloxydim,
tralkoxydim and butroxydim;
- and/or which are resistant to glyphosate;
- and/or which are resistant to one or more ALS inhibitor herbicides (ALS =
acetolactate
synthase), such as one or more sulfonyl urea herbicides (e.g. iodosulfuron-
methyl,
mesosulfuron-methyl, tribenuron-methyl, triasulfuron, prosulfuron,
sulfosulfuron,
pyrazosulfuron-ethyl, bensulfuron-methyl, nicosulfuron, flazasulfuron,
iofensulfuron,
metsulfuron-methyl, or any other sulfonyl urea herbicide disclosed in The
Pesticide Manual,
15th edition, 2009, ed. C.D.S. Tomlin, British Crop Protection Council) and/or
one or more
triazolopyrimidine herbicides (e.g. florasulam, pyroxsulam or penoxsulam)
and/or one or
more pyrimidinyl-(thio or oxy)-benzoate herbicides (e.g. bispyribac-sodium or
pyriftalid)
and/or one or more sulfonylamino-carbonyl-triazolinone herbicides (e.g.
thiencarbazone-
methyl, propoxycarbazone-sodium or flucarbazone-sodium) and/or one or more
imidazolinone herbicides (e.g. imazamox).

- 100 -
Such resistant (in particular ACCase-inhibitor-resistant, glyphosate-
resistant, and/or ALS-
inhibitor-resistant) grassy weeds can more particularly comprise Alopecurus
myosuroides,
Apera spica-venti, Avena fatua, Avena sterilis, Brachiaria decumbens,
Brachiaria
plantaginea, Digitaria horizontalis, Digitaria insularis, Digitaria
sanguinalis, Echinochloa
colona, Echinochloa crus-galli, Eleusine indica, Lolium multiflorum, Lolium
rigidum, Lolium
perenne, Phalaris minor, Phalaris paradoxa, Setaria viridis, Setaria faberi,
Setaria glauca,
and/or Sorghum hale pense.
In an even more particular embodiment of the invention, the compound of
formula (I) can be
applied to grassy monocotyledonous weeds (e.g. selected from one of the above-
mentioned
list(s) of grassy weeds):
(al) which are resistant to one or more ACCase inhibitor herbicides (e.g.
selected from the
above-mentioned list of ACCase inhibitor herbicides) at least partly by means
of mutation
(e.g. substitution) of one or more amino acids on the ACCase target site in
the weed (e.g.
see S.B. Powles and Qin Yu, "Evolution in Action: Plants Resistant to
Herbicides", Annu.
Rev. Plant Biol., 2010, 61, pp. 317-347, e.g. see pages 325-327 therein in
particular Table 3,
for examples of such resistant weeds and/or amino acid
substitutions); and/or
(a2) which are resistant to glyphosate at least partly by means of mutation
(e.g. substitution)
of one or more amino acids on the EPSPS target site in the weed targeted by
glyphosate
(e.g. see above-mentioned S.B. Powles and Qin Yu article, pp. 327-329); and/or
(a3) which are resistant to one or more ALS inhibitor herbicides (e.g.
selected from the
above-mentioned list of ALS inhibitor herbicides) at least partly by mutation
(e.g. substitution)
of one or more amino acids on the ALS target site in the weed (e.g. see S.B.
Powles and Qin
Yu, "Evolution in Action: Plants Resistant to Herbicides", Annu. Rev. Plant
Biol., 2010, 61,
pp. 317-347, e.g. see pages 322-324 therein in particular Table 2,
for examples of such resistant weeds and/or amino acid substitutions); and/or
(b) which are resistant to: one or more ACCase inhibitor herbicides (e.g.
selected from the
above-mentioned list), and/or glyphosate, and/or one or more ALS inhibitor
herbicides (e.g.
selected from the above-mentioned list); at least partly by metabolic-type
herbicidal
resistance e.g. at least partly by cytochrome P450-mediated herbicide
metabolism (e.g. see
S.B. Powles and Qin Yu, "Evolution in Action: Plants Resistant to Herbicides",
Annu. Rev.
Plant Biol., 2010, 61, pp. 317-347, e.g. see Table 4 on page 328).
Date Recue/Date Received 2020-05-25

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Typically, dicotyledonous weeds, e.g. to be controlled, comprise (e.g. are)
Abutilon,
Amaranthus, Chenopodium, Chrysanthemum, Galium, Ipomoea, Kochia, Nasturtium,
Polygonum, Sida, Sinapsis, Solanum, Stellaria, Viola, Veronica and/or
Xanthium.
Areas under cultivation, and/or the locus (e.g. of weeds and/or of crops of
useful plants), are
to be understood as including land where the crop plants are already growing
as well as land
intended for the cultivation of those crop plants.
In all aspects of the invention, the rate of application (typically to the
weeds and/or to the
crops of useful plants and/or to the locus thereof) of the compound of formula
(I) (which
optionally may be an agrochemically acceptable salt thereof) is generally from
1 to 2000 g of
the compound of formula (I) per hectare (ha) (measured as the salt-free
compound, i.e.
excluding the weight of any associated salt counterion(s)), in particular from
5 to 1000 g/ha or
from 5 to 500 g/ha or from 10 to 500 g/ha, preferably from 10 to 400 g/ha or
from 20 to 300
g/ha, of the compound of formula (I) (measured as the salt-free compound, i.e.
excluding the
weight of any associated salt counterion(s)). In a preferred embodiment, the
above rates of
application are for post-emergence application of the compound of formula (I)
(which
optionally may be an agrochemically acceptable salt thereof).
In all aspects of the invention, the compound of formula (I) can be applied
(typically to the
weeds and/or to the crops of useful plants and/or to the locus thereof) pre-
and/or post-
emergence, but preferably is applied post-emergence.
Other possible uses ¨ e.g. possible insecticidal and/or acaricidal uses
The main use and purpose of the compounds of formula (I) according to the
invention is their
herbicidal use. However, at least some of the compounds of formula (I) may
have activity
against one or more types of pest (in particular pests associated with
agriculture and/or food
storage). For example, at least some of the compounds of formula (I) may have
at least
some insecticidal, acaricidal, molluscicidal and/or nematicidal activity.
At least some of the compounds of formula (I) may have activity against
(and/or may help to
control and/or combat) insect pests, such as one or more of: Coleoptera,
Dictyoptera,

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Diptera, Hemiptera (including Homoptera), Hymenoptera, Isoptera, Lepidoptera,
Orthoptera,
Siphonaptera and/or Thysanoptera.
At least some of the compounds of formula (I) may have activity against
(and/or may help to
control and/or combat) acarine pests and/or pests from the order Acarina, such
as one or
more of: Acalitus spp, Aculus spp, Acaricalus spp, Aceria spp, Acarus siro,
Amblyomma
spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia spp,
Calipitrimerus spp.,
Chorioptes spp., Dermanyssus gallinae, Dermatophagoides spp, Eotetranychus
spp,
Eriophyes spp., Hemitarsonemus spp, Hyalomma spp., lxodes spp., Olygonychus
spp,
Ornithodoros spp., Polyphagotarsone latus, Panonychus spp., Phyllocoptruta
oleivora,
Phytonemus spp, Polyphagotarsonemus spp, Psoroptes spp., Rhipicephalus spp.,
Rhizoglyphus spp., Sarcoptes spp., Steneotarsonemus spp, Tarsonemus spp.
and/or
Tetranychus spp.
At least some of the compounds of formula (I) may have activity against
(and/or may help to
control and/or combat) other (i.e. non-insect, non-acarine) invertebrate
pests, for example,
nematode and/or mollusc pests.
Insects, acarines, nematodes and/or molluscs are hereinafter collectively
referred to as
pests.
Examples of pest species, on and/or to which the compounds of formula (I) can
be tried
and/or applied, include one or more of: Myzus spp. such as Myzus persicae
(aphid), Aphis
spp. such as Aphis gossypii (aphid) or Aphis fabae (aphid), Lygus spp.
(capsids), Dysdercus
spp. (capsids), Nilaparvata lugens (planthopper), Nephotettixc incticeps
(leafhopper), Nezara
spp. (stinkbugs), Euschistus spp. (stinkbugs), Leptocorisa spp. (stinkbugs),
Frankliniella
occidentalis (thrip), Thrips spp. (thrips), Leptinotarsa decemlineata
(Colorado potato beetle),
Anthonomus grandis (boll weevil), Aonidiella spp. (scale insects),
Trialeurodes spp. (white
flies), Bemisia tabaci (white fly), Ostrinia nubilalis (European corn borer),
Spodoptera littoralis
(cotton leafworm), Heliothis virescens (tobacco budworm), Helicoverpa armigera
(cotton
bollworm), Helicoverpa zea (cotton bollworm), Sylepta derogata (cotton leaf
roller), Pieris
brassicae (white butterfly), Pluto//a xylostella (diamond back moth), Agrotis
spp. (cutworms),
Chilo suppressalis (rice stem borer), Locusta_migratoria (locust),
Chortiocetes terminifera
(locust), Diabrotica spp. (rootworms), Panonychus ulmi (European red mite),
Panonychus
citri (citrus red mite), Tetranychus spp. such as Tetranychus urticae (two-
spotted spider mite)

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or Tetranychus cinnabarinus (carmine spider mite), Phyllocoptruta oleivora
(citrus rust mite),
Polyphagotarsonemus latus (broad mite), Brevipalpus spp. (flat mites),
Boophilus microplus
(cattle tick), Dermacentor variabilis (American dog tick), Ctenocephalides
fells (cat flea),
Liriomyza spp. (leafminer), Musca domestica (housefly), Aedes aegypti
(mosquito),
Anopheles spp. (mosquitoes), Culex spp. (mosquitoes), Lucillia spp.
(blowflies), Blatt&la
germanica (cockroach), Periplaneta americana (cockroach), Blatta orientalis
(cockroach),
termites of the Mastotermitidae (for example Mastotermes spp.), of the
Kalotermitidae (for
example Neotermes spp.), of the Rhinotermitidae (for example Coptotermes
formosanus,
Reticulitermes flavipes, R. speratu, R. virginicus, R. hesperus, or R.
santonensis) or of the
Termitidae (for example Globitermes sulphureus), Solenopsis geminata (fire
ant),
Monomorium pharaonis (pharaoh's ant), Damalinia spp. or Linognathus spp.
(biting lice or
sucking lice), Meloidogyne spp. (root knot nematodes), Globodera spp. or
Heterodera spp.
(cyst nematodes), Pratylenchus spp. (lesion nematodes), Rhodopholus spp.
(banana
burrowing nematodes), Tylenchulus spp.(citrus nematodes), Haemonchus contortus
(barber
pole worm), Caenorhabditis elegans (vinegar eelworm), Trichostrongylus spp.
(gastro
intestinal nematodes) and/or Deroceras reticulatum (slug).
Combinations and mixtures
In a further aspect, the present invention provides a herbicidal composition,
e.g. for use in a
method of controlling weeds (e.g. monocotyledonous such as grassy weeds) in
crops of
useful plants, comprising a compound of formula (I) as defined herein (e.g. a
herbicidally
effective amount thereof), and an agrochemically acceptable carrier, diluent
and/or solvent,
and also comprising one or more further herbicides, and/or a safener.
In all aspects of the invention, the compound of the formula (I) is optionally
present (e.g.
where chemically possible) as an agrochemically acceptable salt thereof.
Examples of these mixtures / compositions, comprising one or more further
herbicides and/or
a safener, follow.
The compounds of formula (I) according to the invention can be used in
combination with
one or more further herbicides, e.g. as mixture partner(s) for the compound of
formula (I).

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Preferably, in these mixtures (in particular in the specific mixtures
disclosed hereinbelow),
the compound of the formula (I) is one of those compounds listed in Tables 1
to 25 01 26 or
27 and/or one of the exemplified compounds (e.g. A-1 to A-18, or A-19 to A-41,
or P-3 to
P-7) as disclosed herein e.g. hereinbelow.
In particular, the following mixtures of the compound of formula (I) with one
or more further
herbicides are particularly disclosed:
compound of formula I + acetochlor, compound of formula I + acifluorfen,
compound of
formula I + acifluorfen-sodium, compound of formula I + aclonifen, compound of
formula I +
acrolein, compound of formula I + alachlor, compound of formula I + alloxydim,
compound of
formula I + allyl alcohol, compound of formula I + ametryn, compound of
formula I +
amicarbazone, compound of formula I + amidosulfuron, compound of formula I +
aminopyralid, compound of formula I + amitrole, compound of formula I +
ammonium
sulfamate, compound of formula I + anilofos, compound of formula I + asulam,
compound of
formula I + atraton, compound of formula I + atrazine, compound of formula I +
azimsulfuron,
compound of formula I + BCPC, compound of formula I + beflubutamid, compound
of formula
I + benazolin, compound of formula I + benfluralin, compound of formula I +
benfuresate,
compound of formula I + bensulfuron, compound of formula I + bensulfuron-
methyl,
compound of formula I + bensulide, compound of formula I + bentazone, compound
of
formula I + benzfendizone, compound of formula I + benzobicyclon, compound of
formula I +
benzofenap, compound of formula I + bifenox, compound of formula I +
bilanafos, compound
of formula I + bispyribac, compound of formula I + bispyribac-sodium, compound
of formula I
+ borax, compound of formula I + bromacil, compound of formula I +
bromobutide, compound
of formula I + bromoxynil, compound of formula I + bromoxynil heptanoate,
compound of
formula I + bromoxynil octanoate, compound of formula I + bromoxynil
heptanoate +
bromoxynil octanoate, compound of formula I + butachlor, compound of formula I
+
butafenacil, compound of formula I + butamifos, compound of formula I +
butralin, compound
of formula I + butroxydim, compound of formula I + butylate, compound of
formula I +
cacodylic acid, compound of formula I + calcium chlorate, compound of formula
I +
cafenstrole, compound of formula I + carbetamide, compound of formula I +
carfentrazone,
compound of formula I + carfentrazone-ethyl, compound of formula I + CDEA,
compound of
formula I + CEPC, compound of formula I + chloransulam, compound of formula I
+
chloransulam-methyl, compound of formula I + chlorflurenol, compound of
formula I +

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chlorflurenol-methyl, compound of formula I + chloridazon, compound of formula
I +
chlorimuron, compound of formula I + chlorimuron-ethyl, compound of formula I
+
chloroacetic acid, compound of formula I + chlorotoluron, compound of formula
I +
chlorpropham, compound of formula I + chlorsulfuron, compound of formula I +
chlorthal,
compound of formula I + chlorthal-dimethyl, compound of formula I + cinidon-
ethyl,
compound of formula I + cinmethylin, compound of formula I + cinosulfuron,
compound of
formula I + cisanilide, compound of formula I + clethodim, compound of formula
I +
clodinafop, compound of formula I + clodinafop-propargyl, compound of formula
I +
clomazone, compound of formula I + clomeprop, compound of formula I +
clopyralid,
compound of formula I + cloransulam, compound of formula I + cloransulam-
methyl,
compound of formula I + CMA, compound of formula I + 4-CPB, compound of
formula I +
CPMF, compound of formula I + 4-CPP, compound of formula I + CPPC, compound of
formula I + cresol, compound of formula I + cumyluron, compound of formula I +
cyanamide,
compound of formula I + cyanazine, compound of formula I + cycloate, compound
of formula
I + cyclosulfamuron, compound of formula I + cycloxydim, compound of formula I
+
cyhalofop, compound of formula I + cyhalofop-butyl, compound of formula I +
2,4-D,
compound of formula I + 2,4-D-dimethylammonium, compound of formula I +
2,4-D-2-ethylhexyl, compound of formula I + a choline salt of 2,4-D (see e.g.
Examples 2 and
3 of W02010/123871A1), compound of formula I + 2,4-D + glyphosate, compound of
formula
.. I + 2,4-D-dimethylammonium + glyphosate, compound of formula I + 2,4-D-2-
ethylhexyl +
glyphosate, compound of formula I + a choline salt of 2,4-D + glyphosate (see
e.g. Examples
2 and 3 of W02010/123871A1), compound of formula I + 3,4-DA, compound of
formula I +
daimuron, compound of formula I + dalapon, compound of formula I + dazomet,
compound of
formula I + 2,4-DB, compound of formula I + 3,4-DB, compound of formula I +
2,4-DEB,
compound of formula I + desmedipham, compound of formula I + dicamba, compound
of
formula I + dicamba-dimethylammonium, compound of formula I + dicamba-
potassium,
compound of formula I + dicamba-sodium, compound of formula I + dicamba-
diglycolamine,
compound of formula I + a N,N-bisqaminopropyl]methylamine salt of dicamba (see
e.g.
US2012/0184434A1), compound of formula I + dicamba + glyphosate, compound of
formula
I + dicamba-dimethylammonium + glyphosate, compound of formula I + dicamba-
potassium
+ glyphosate, compound of formula I + dicamba-sodium + glyphosate, compound of
formula I
+ dicamba-diglycolamine + glyphosate, compound of formula I + a N,N-bis-
[aminopropyl]methylamine salt of dicamba + glyphosate, compound of formula I +
dichlobenil, compound of formula I + ortho-dichlorobenzene, compound of
formula I + para-

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dichlorobenzene, compound of formula I + dichlorprop, compound of formula I +
dichlorprop-
P, compound of formula I + diclofop, compound of formula I + diclofop-methyl,
compound of
formula I + diclosulam, compound of formula I + difenzoquat, compound of
formula I +
difenzoquat metilsulfate, compound of formula I + diflufenican, compound of
formula I +
diflufenzopyr, compound of formula I + dimefuron, compound of formula I +
dimepiperate,
compound of formula I + dimethachlor, compound of formula I + dimethametryn,
compound
of formula I + dimethenamid, compound of formula I + dimethenamid-P, compound
of
formula I + dimethipin, compound of formula I + dimethylarsinic acid, compound
of formula I
+ dinitramine, compound of formula I + dinoterb, compound of formula I +
diphenamid,
.. compound of formula I + diquat, compound of formula I + diquat dibromide,
compound of
formula I + dithiopyr, compound of formula I + diuron, compound of formula I +
DNOC,
compound of formula I + 3,4-DP, compound of formula I + DSMA, compound of
formula I +
EBEP, compound of formula I + endothal, compound of formula I + EPTC, compound
of
formula I + esprocarb, compound of formula I + ethalfluralin, compound of
formula I +
ethametsulfuron, compound of formula I + ethametsulfuron-methyl, compound of
formula I +
ethofumesate, compound of formula I + ethoxyfen, compound of formula I +
ethoxysulfuron,
compound of formula I + etobenzanid, compound of formula (I) + fenoxaprop,
compound of
formula (I) + fenoxaprop-ethyl, compound of formula I + fenoxaprop-P, compound
of formula
I + fenoxaprop-P-ethyl, compound of formula I + fenoxasulfone (CAS Reg. No.
639826-16-7),
compound of formula I + fentrazamide, compound of formula I + ferrous sulfate,
compound of
formula I + flamprop-M, compound of formula I + flazasulfuron, compound of
formula I +
florasulam, compound of formula I + fluazifop, compound of formula I +
fluazifop-butyl,
compound of formula I + fluazifop-P, compound of formula I + fluazifop-P-
butyl, compound of
formula I + flucarbazone, compound of formula I + flucarbazone-sodium,
compound of
.. formula I + flucetosulfuron, compound of formula I + fluchloralin, compound
of formula I +
flufenacet, compound of formula I + flufenpyr, compound of formula I +
flufenpyr-ethyl,
compound of formula I + flumetsulam, compound of formula I + flumiclorac,
compound of
formula I + flumiclorac-pentyl, compound of formula I + flumioxazin, compound
of formula I +
fluometuron, compound of formula I + fluoroglycofen, compound of formula I +
fluoroglycofen-ethyl, compound of formula I + flupropanate, compound of
formula I +
flupyrsulfuron, compound of formula I + flupyrsulfuron-methyl-sodium, compound
of formula I
+ flurenol, compound of formula I + fluridone, compound of formula I +
flurochloridone,
compound of formula I + fluroxypyr, compound of formula I + fluroxypyr-meptyl,
compound of
formula I + fluroxypyr-butometyl, compound of formula I + flurtamone, compound
of formula I

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+ fluthiacet, compound of formula I + fluthiacet-methyl, compound of formula I
+ fomesafen,
compound of formula I + foramsulfuron, compound of formula I + fosamine,
compound of
formula I + glufosinate, compound of formula I + glufosinate-ammonium,
compound of
formula I + glufosinate-P, compound of formula I + glyphosate, compound of
formula I +
glyphosate-diammonium, compound of formula I + glyphosate-isopropylammonium,
compound of formula I + glyphosate-potassium, compound of formula I +
halosulfuron,
compound of formula I + halosulfuron-methyl, compound of formula I +
haloxyfop, compound
of formula I + haloxyfop-P, compound of formula (I) + haloxyfop-methyl,
compound of
formula (I) + haloxyfop-P-methyl, compound of formula I + HC-252, compound of
formula I +
hexazinone, compound of formula I + imazamethabenz, compound of formula I +
imazamethabenz-methyl, compound of formula I + imazamox, compound of formula I
+
imazapic, compound of formula I + imazapyr, compound of formula I + imazaquin,
compound
of formula I + imazethapyr, compound of formula I + imazosulfuron, compound of
formula I +
indanofan, compound of formula I + iodomethane, compound of formula I +
iodosulfuron,
compound of formula I + iodosulfuron-methyl-sodium, compound of formula I +
ioxynil,
compound of formula I + ipfencarbazone (CAS Reg. No. 212201-70-2), compound of
formula
I + isoproturon, compound of formula I + isouron, compound of formula I +
isoxaben,
compound of formula I + isoxachlortole, compound of formula I + isoxaflutole,
compound of
formula I + karbutilate, compound of formula I + lactofen, compound of formula
I + lenacil,
compound of formula I + linuron, compound of formula I + MAA, compound of
formula I +
MAMA, compound of formula I + MCPA, compound of formula I + MCPA-thioethyl,
compound of formula I + MCPB, compound of formula I + mecoprop, compound of
formula I
+ mecoprop-P, compound of formula I + mefenacet, compound of formula I +
mefluidide,
compound of formula I + mesosulfuron, compound of formula I + mesosulfuron-
methyl,
compound of formula I + mesotrione, compound of formula I + metam, compound of
formula
I + metamifop, compound of formula I + metamitron, compound of formula I +
metazachlor,
compound of formula I + metazosulfuron (NC-620, CAS Reg. No. 868680-84-6),
compound
of formula I + methabenzthiazuron, compound of formula I + methylarsonic acid,
compound
of formula I + methyldymron, compound of formula I + methyl isothiocyanate,
compound of
formula I + metobenzuron, compound of formula I + metolachlor, compound of
formula I + S-
metolachlor, compound of formula I + metosulam, compound of formula I +
metoxuron,
compound of formula I + metribuzin, compound of formula I + metsulfuron,
compound of
formula I + metsulfuron-methyl, compound of formula I + MK-616, compound of
formula I +
molinate, compound of formula I + monolinuron, compound of formula I + MSMA,
compound

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of formula I + naproanilide, compound of formula I + napropamide, compound of
formula I +
naptalam, compound of formula I + neburon, compound of formula I +
nicosulfuron,
compound of formula I + nonanoic acid, compound of formula I + norflurazon,
compound of
formula I + oleic acid (fatty acids), compound of formula I + orbencarb,
compound of formula
I + orthosulfamuron, compound of formula I + oryzalin, compound of formula I +
oxadiargyl,
compound of formula I + oxadiazon, compound of formula I + oxasulfuron,
compound of
formula I + oxaziclomefone, compound of formula I + oxyfluorfen, compound of
formula I +
paraquat, compound of formula I + paraquat dichloride, compound of formula I +
pebulate,
compound of formula I + pendimethalin, compound of formula I + penoxsulam,
compound of
formula I + pentachlorophenol, compound of formula I + pentanochlor, compound
of formula I
+ pentoxazone, compound of formula I + pethoxamid, compound of formula I +
petrolium oils,
compound of formula I + phenmedipham, compound of formula I + phenmedipham-
ethyl,
compound of formula I + picloram, compound of formula I + picolinafen,
compound of
formula I + pinoxaden, compound of formula I + piperophos, compound of formula
I +
potassium arsenite, compound of formula I + potassium azide, compound of
formula I +
pretilachlor, compound of formula I + primisulfuron, compound of formula I +
primisulfuron-
methyl, compound of formula I + prodiamine, compound of formula I +
profluazol, compound
of formula I + profoxydim, compound of formula I + prometon, compound of
formula I +
prometryn, compound of formula I + propachlor, compound of formula I +
propanil,
compound of formula I + propaquizafop, compound of formula I + propazine,
compound of
formula I + propham, compound of formula I + propisochlor, compound of formula
I +
propoxycarbazone, compound of formula I + propoxycarbazone-sodium, compound of
formula I + propyrisulfuron (TH-547, CAS Reg. No. 570415-88-2), compound of
formula I +
propyzamide, compound of formula I + prosulfocarb, compound of formula I +
prosulfuron,
compound of formula I + pyraclonil, compound of formula I + pyraflufen,
compound of
formula I + pyraflufen-ethyl, compound of formula I + pyrazolynate, compound
of formula I +
pyrazosulfuron, compound of formula I + pyrazosulfuron-ethyl, compound of
formula I +
pyrazoxyfen, compound of formula I + pyribenzoxim, compound of formula I +
pyributicarb,
compound of formula I + pyridafol, compound of formula I + pyridate, compound
of formula I
+ pyriftalid, compound of formula I + pyriminobac, compound of formula I +
pyriminobac-
methyl, compound of formula I + pyrimisulfan, compound of formula I +
pyrithiobac,
compound of formula I + pyrithiobac-sodium, compound of formula I +
quinclorac, compound
of formula I + quinmerac, compound of formula I + quinoclamine, compound of
formula I +
quizalofop, compound of formula I + quizalofop-ethyl, compound of formula I +
quizalofop-P,

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compound of formula I + quizalofop-P-ethyl, compound of formula! + quizalofop-
P-tefuryl,
compound of formula I + rimsulfuron, compound of formula! + sethoxydim,
compound of
formula 1+ siduron, compound of formula! + simazine, compound of formula! +
simetryn,
compound of formula I + SMA, compound of formula 1 + sodium arsenite, compound
of
formula 1+ sodium azide, compound of formula 1 + sodium chlorate, compound of
formula 1 +
sulcotrione, compound of formula! + sulfentrazone, compound of formula 1 +
sulfometuron,
compound of formula I + sulfometuron-methyl, compound of formula 1 +
sulfosate, compound
of formula 1+ sulfosulfuron, compound of formula 1 + sulfuric acid, compound
of formula 1 +
tar oils, compound of formula! + 2,3,6-TBA, compound of formula! + TCA,
compound of
formula 1+ TCA-sodium, compound of formula 1+ tebuthiuron, compound of
formula! +
tepraloxydim, compound of formula! + terbacil, compound of formula! +
terbumeton,
compound of formula I + terbuthylazine, compound of formula 1+ terbutryn,
compound of
formula 1+ thenylchlor, compound of formula 1 + thiazopyr, compound of formula
1 +
thifensulfuron, compound of formula! + thifensulfuron-methyl, compound of
formula 1+
thiobencarb, compound of formula! + tiocarbazil, compound of formula! +
topramezone,
compound of formula I + tralkoxydim, compound of formula! + tri-allate,
compound of
formula 1+ triasulfuron, compound of formula 1 + triaziflam, compound of
formula 1 +
tribenuron, compound of formula 1+ tribenuron-methyl, compound of formula! +
tricamba,
compound of formula I + triclopyr, compound of formula 1 + trietazine,
compound of formula!
+ trifloxysulfuron, compound of formula I + trifloxysulfuron-sodium, compound
of formula I +
trifluralin, compound of formula 1+ triflusulfuron, compound of formula 1 +
triflusulfuron-
methyl, compound of formula! + trihydroxytriazine, compound of formula! +
tritosulfuron,
compound of formula I + [342-chloro-4-fluoro-5-(1-methy1-6-trifluoromethy1-2,4-
dioxo-1,2,3,4-
tetrahydropyrimidin-3-y1)phenoxy]-2-pyridyloxy]acetic acid ethyl ester (CAS
Reg. No.
353292-31-6), compound of formula 1 + 4-[(4,5-dihydro-3-methoxy-4-methy1-5-
oxo)-1H-1,2,4-
triazol-1-ylcarbonylsulfamoyl]-5-methylthiophene-3-carboxylic acid (BAY636),
compound of
formula 1+ BAY747 (CAS Reg. No. 335104-84-2), compound of formula 1 +
topramezone
(CAS Reg. No. 210631-68-8), compound of formula 1+ 4-hydroxy-3-[[24(2-
methoxyethoxy)-
methyl]-6-(trifluoromethyl)-3-pyridinyl]carbonylFbicyclo[3.2.1]oct-3-en-2-one
(which is
bicyclopyrone, CAS Reg. No. 352010-68-5), compound of formula 1 + 4-hydroxy-
34[2-(3-
methoxypropy1)-6-(difluoromethyl)-3-pyridinyl]carbonyl]-bicyclo[3.2.1]oct-3-en-
2-one,
compound of formula (1) + 4-(4'-chloro-4-cyclopropy1-2'-fluorobipheny1-3-y1)-
2,2,6,6-
tetramethy1-2H-pyran-3,5(4H,6H)-dione (which is the compound of Example P8
disclosed on
pages 31-32 and 35-36 of WO 2010/136431 A9 (Syngenta Limited), and which is
also

- 110 -
compound A-13 disclosed in pages 4, 5, 7 and 11 of WO 2011/073616 A2 (Syngenta
Limited),
compound of formula (1) + 4-(2',4'-dichloro-4-cyclopropylbipheny1-3-y1)-
2,2,6,6-tetramethyl-
2H-pyran-3,5(4H,6H)-dione (which is the compound of Example P9 disclosed on
pages 36-
37 and 40-41 of WO 2010/136431 A9 (Syngenta Limited), and which is also
compound A-12
disclosed in page 10 of WO 2011/073616 A2 (Syngenta Limited),
compound of formula (1) + 4-(4'-chloro-
4-ethy1-2'-fluorobipheny1-3-y1)-2,2,6,6-tetramethyl-2H-pyran-3,5(4H,6H)-dione
(which is
compound A-66 disclosed on page 95 of WO 2008/071405 Al (Syngenta
Participations AG
.. and Syngenta Limited), and which is also compound A-4 disclosed on page 7
of WO
2011/073615A2 (Syngenta Limited),
compound of formula (1) + 4-(2',4'-dichloro-4-ethylbipheny1-3-y1)-2,2,6,6-
tetramethy1-2H-pyran-3,5(4H,6H)-dione (which is compound A-45 disclosed on
page 93 of
WO 2008/071405 Al (Syngenta Participations AG and Syngenta Limited), and which
is also
the compound of Example P10 disclosed on pages 41 and 45 of WO 2010/136431 A9
(Syngenta Limited), and which is also compound A-7 disclosed on page 7 of WO
2011/073615 A2 (Syngenta Limited),
compound of formula (1) + 4-(2',4'-dichloro-4-ethylbipheny1-3-y1)-5-
(methoxycarbonyloxy)-2,2,6,6-tetramethy1-2H-pyran-3(6H)-one (which is compound
D-26
disclosed on page 231 of WO 2008/071405 Al (Syngenta Participations AG and
Syngenta
Limited), and which is also compound A-9 disclosed on page 8 of WO 2011/073615
A2
(Syngenta Limited),
compound of formula (1) + one of the specific herbicidal compounds disclosed
in
WO 2010/059676 (Dow, e.g. as defined in one of the examples therein and/or
e.g. can be
plus cloquintocet-mexyl as safener)
, compound of formula (1) + one of the specific herbicidal compounds disclosed
in
WO 2010/059680 (Dow, e.g. as defined in one of the examples therein and/or
e.g. can be
plus cloquintocet-mexyl or another safener)
, and compound of formula (I) + one of the specific herbicidal compounds
disclosed
in WO 2010/059671 (Dow, e.g. as defined in one of the examples therein and/or
e.g. can be
plus a safener) , compound of
formula 1+ halauxifen (which is 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-
methoxyphenyl)pyridine-2-carboxylic acid, CAS Reg. No. 943832-60-8), compound
of
formula 1+ halauxifen-methyl (which is methyl 4-amino-3-chloro-6-(4-chloro-2-
fluoro-3-
Date Recue/Date Received 2020-05-25

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- 11 1 -
methoxyphenyl)pyridine-2-carboxylate, CAS Reg. No. 943831-98-9), compound of
formula I
+ aminocyclopyrachlor (which is 6-amino-5-chloro-2-cyclopropylpyrimidine-4-
carboxylic acid,
CAS Reg. No. 858956-08-8), compound of formula I + aminocyclopyrachlor-methyl
(which is
methyl 6-amino-5-chloro-2-cyclopropylpyrimidine-4-carboxylate, CAS Reg. No.
858954-83-
3), compound of formula I + aminocyclopyrachlor-potassium (which is potassium
6-amino-5-
chloro-2-cyclopropylpyrimidine-4-carboxylate, CAS Reg. No. 858956-35-1),
compound of
formula I + saflufenacil (which is N'-{2-chloro-4-fluoro-541,2,3,6-tetrahydro-
3-methy1-2,6-
dioxo-4-(trifluoromethyl)pyrimidin-1-yl]benzoyll-N-isopropyl-N-
methylsulfamide, CAS Reg.
No. 372137-35-4), compound of formula I + iofensulfuron (which is 1-(2-
iodophenylsulfonyI)-
3-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)urea, CAS Reg. No. 1144097-22-2),
compound of
formula I + iofensulfuron-sodium (which is sodium N-(2-iodophenylsulfony1)-/V-
(4-methoxy-6-
methyl-1,3,5-triazin-2-y1)carbamimidate, CAS Reg. No. 1144097-30-2), compound
of formula
I + clacyfos (which is dimethyl R1RS)-1-(2,4-
dichlorophenoxyacetoxy)ethyl]phosphonate,
also named Ivxiancaolin or luxiancaolin, CAS Reg. No. 215655-76-8), compound
of formula I
+ cyclopyrimorate (which is 6-chloro-3-(2-cyclopropy1-6-
methylphenoxy)pyridazin-4-y1
morpholine-4-carboxylate, CAS Reg. No. 499231-24-2), or compound of formula I
+
triafamone (which is N42-[(4,6-dimethoxy-1,3,5-triazin-2-yl)carbony1]-6-
fluoropheny1]-N-
methy1-1,1-difluoromethanesulfonamide, CAS Reg. No. 874195-61-6).
The mixture partners for the compound of formula (I) are optionally in the
form of an ester (in
particular an agrochemically acceptable ester) or a salt (in particular an
agrochemically
acceptable salt) thereof (e.g. where chemically possible). The above-mentioned
mixture
partners for the compound of formula (I), are generally mentioned e.g. in The
Pesticide
Manual, 15th Edition, 2009, ed. C.D.S. Tomlin, British Crop Production
Council.
In the present patent specification, "CAS Reg. No." or "CAS RN" means the
Chemical
Abstracts Service Registry Number of the stated compound.
For applications in cereals, the following mixtures are preferred: compound of
formula I +
aclonifen, compound of formula I + amidosulfuron, compound of formula I +
aminopyralid,
compound of formula I + beflubutamid, compound of formula I + benfluralin,
compound of
formula I + bifenox, compound of formula I + bromoxynil, compound of formula I
+ bromoxynil
heptanoate, compound of formula I + bromoxynil octanoate, compound of formula
I +
bromoxynil heptanoate + bromoxynil octanoate, compound of formula I +
butafenacil,
compound of formula I + carbetamide, compound of formula I + carfentrazone,
compound of

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formula I + carfentrazone-ethyl, compound of formula I + chlorotoluron,
compound of formula
I + chlorpropham, compound of formula I + chlorsulfuron, compound of formula I
+ cinidon-
ethyl, compound of formula I + clodinafop, compound of formula I + clodinafop-
propargyl,
compound of formula I + clopyralid, compound of formula I + 2,4-D, compound of
formula I +
2,4-D-dimethylammonium, compound of formula I + 2,4-D-2-ethylhexyl, compound
of formula
I + a choline salt of 2,4-D (see e.g. Examples 2 and 3 of W02010/123871A1),
compound of
formula I + dicamba, compound of formula I + dicamba-dimethylammonium,
compound of
formula I + dicamba-potassium, compound of formula I + dicamba-sodium,
compound of
formula I + dicamba-diglycolamine, compound of formula I + a N,N-bis-
.. [aminopropyl]methylamine salt of dicamba (see e.g. US2012/0184434A1),
compound of
formula I + dichlobenil, compound of formula I + dichlorprop, compound of
formula I +
diclofop, compound of formula I + diclofop-methyl, compound of formula I +
difenzoquat,
compound of formula I + difenzoquat metilsulfate, compound of formula I +
diflufenican,
compound of formula I + diquat, compound of formula I + diquat dibromide,
compound of
formula (I) + fenoxaprop, compound of formula (I) + fenoxaprop-ethyl, compound
of formula I
+ fenoxaprop-P, compound of formula I + fenoxaprop-P-ethyl, compound of
formula I +
flamprop-M, compound of formula I + florasulam, compound of formula I +
fluazifop-P-butyl,
compound of formula I + flucarbazone, compound of formula I + flucarbazone-
sodium,
compound of formula I + flufenacet, compound of formula I + flupyrsulfuron,
compound of
formula I + flupyrsulfuron-methyl-sodium, compound of formula I +
flurochloridone,
compound of formula I + fluroxypyr, compound of formula I + fluroxypyr-meptyl,
compound of
formula I + fluroxypyr-butometyl, compound of formula I + flurtamone, compound
of formula I
+ imazamethabenz-methyl, compound of formula I + imazamox, compound of formula
I +
iodosulfuron, compound of formula I + iodosulfuron-methyl-sodium, compound of
formula I +
ioxynil, compound of formula I + isoproturon, compound of formula I + linuron,
compound of
formula I + MCPA, compound of formula I + mecoprop, compound of formula I +
mecoprop-
P, compound of formula I + mesosulfuron, compound of formula I + mesosulfuron-
methyl,
compound of formula I + mesotrione, compound of formula I + metribuzin,
compound of
formula I + metsulfuron, compound of formula I + metsulfuron-methyl, compound
of formula I
+ pendimethalin, compound of formula I + picolinafen, compound of formula I +
pinoxaden,
compound of formula I + prodiamine, compound of formula I + propanil, compound
of formula
I + propoxycarbazone, compound of formula I + propoxycarbazone-sodium,
compound of
formula I + prosulfocarb, compound of formula I + pyrasulfotole, compound of
formula I +
pyridate, compound of formula I + pyroxasulfone (KIN-485), compound of formula
I +

- 113 -
pyroxsulam compound of formula I + sulfosulfuron, compound of formula 1 +
tembotrione,
compound of formula I + terbutryn, compound of formula I + thifensulfuron,
compound of
formula I + thiencarbazone, compound of formula I + thifensulfuron-methyl,
compound of
formula I + topramezone, compound of formula I + tralkoxydim, compound of
formula I + tri-
.. allate, compound of formula I + triasulfuron, compound of formula I +
tribenuron, compound
of formula I + tribenuron-methyl, compound of formula I + trifluralin,
compound of formula I +
trinexapac-ethyl and compound of formula I + tritosulfuron, compound of
formula I + 4-
hydroxy-34[24(2-methoxyethoxy)methyl]-6-(trifluoromethyl)-3-
pyridinyl]carbonyl]-
bicyclo[3.2.1]oct-3-en-2-one (which is bicyclopyrone, CAS Reg. No. 352010-68-
5),
.. compound of formula (I) + one of the specific herbicidal compounds
disclosed in WO
2010/059676 (Dow, e.g. as defined in one of the examples therein and/or e.g.
can be plus
cloquintocet-mexyl as safener)
compound of formula (I) + one of the specific herbicidal compounds disclosed
in WO
2010/059680 (Dow, e.g. as defined in one of the examples therein and/or e.g.
can be plus
.. cloquintocet-mexyl or another safener)
, compound of formula I + halauxifen (which is 4-amino-3-chloro-6-(4-chloro-2-
fluoro-3-methoxyphenyl)pyridine-2-carboxylic acid, CAS Reg. No. 943832-60-8),
compound
of formula I + halauxifen-methyl (which is methyl 4-amino-3-chloro-6-(4-chloro-
2-fluoro-3-
methoxyphenyl)pyridine-2-carboxylate, CAS Reg. No. 943831-98-9), compound of
formula I
.. + iofensulfuron (which is 1-(2-iodophenylsulfony1)-3-(4-methoxy-6-methyl-
1,3,5-triazin-2-
yOurea, CAS Reg. No. 1144097-22-2), or compound of formula I + iofensulfuron-
sodium
(which is sodium N-(2-iodophenylsulfonyI)-N'-(4-methoxy-6-methyl-1,3,5-triazin-
2-
yl)carbamimidate, CAS Reg. No. 1144097-30-2);
wherein the mixture partners for the compound of formula (I) may optionally be
in the form of
.. an ester (in particular an agrochemically acceptable ester) or a salt (in
particular an
agrochemically acceptable salt) thereof (e.g. where chemically possible).
For applications in cereals, more preferred is a mixture comprising: a
compound of formula
(I) + amidosulfuron, compound of formula (I) + aminopyralid, compound of
formula (I) +
.. beflubutamid, compound of formula (I) + bromoxynil, compound of formula (I)
+ bromoxynil
heptanoate, compound of formula (I) + bromoxynil octanoate, compound of
formula (I) +
bromoxynil heptanoate + bromoxynil octanoate, compound of formula (I) +
carfentrazone,
compound of formula (I) + carfentrazone-ethyl, compound of formula (I) +
chlorotoluron,
compound of formula (I) + chlorsulfuron, compound of formula (I) + clodinafop,
compound of
Date Recue/Date Received 2020-05-25

- 114 -
formula (I) + clodinafop-propargyl, compound of formula (I) + clopyralid,
compound of
formula (I) + 2,4-D, compound of formula (I) + 2,4-D-dimethylammonium,
compound of
formula (I) + 2,4-D-2-ethylhexyl, compound of formula (I) + a choline salt of
2,4-D (see e.g.
Examples 2 and 3 of W02010/123871A1), compound of formula (I) + dicamba,
compound of
formula (I) + dicamba, compound of formula (I) + dicamba-dimethylammonium,
compound of
formula (I) + dicamba-potassium, compound of formula (I) + dicamba-sodium,
compound of
formula (I) + dicamba-diglycolamine, compound of formula (I) + a N,N-bis-
[aminopropyl]nethylamine salt of dicamba (see e.g. US2012/0184434A1), compound
of
formula (I) + difenzoquat, compound of formula (I) + difenzoquat metilsulfate,
compound of
formula (I) + diflufenican, compound of formula (I) + fenoxaprop-P, compound
of formula (I) +
fenoxaprop-P-ethyl, compound of formula (I) + florasulam, compound of formula
(I) +
flucarbazone, compound of formula (I) + flucarbazone-sodium, compound of
formula (I) +
flufenacet, compound of formula (I) + flupyrsulfuron, compound of formula (I)
+
flupyrsulfuron-methyl-sodium, compound of formula (I) + fluroxypyr, compound
of formula I +
.. fluroxypyr-meptyl, compound of formula I + fluroxypyr-butometyl, compound
of formula (I) +
flurtamone, compound of formula (I) + iodosulfuron, compound of formula (I) +
iodosulfuron-
methyl-sodium, compound of formula (I) + MCPA, compound of formula (I) +
mesosulfuron,
compound of formula (I) + mesosulfuron-methyl, compound of formula (I) +
metsulfuron,
compound of formula (I) + metsulfuron-methyl, compound of formula (I) +
pendimethalin,
compound of formula (I) + picolinafen, compound of formula (I) + pinoxaden,
compound of
formula (I) + prosulfocarb, compound of formula (I) + pyrasulfotole, compound
of formula (I) +
pyroxasulfone (KIN-485), compound of formula (I) + pyroxsulam, compound of
formula (I) +
sulfosulfuron, compound of formula (I) + thifensulfuron, compound of formula
(I) +
thifensulfuron-methyl, compound of formula I + topramezone, compound of
formula (I) +
tralkoxydim, compound of formula (I) + triasulfuron, compound of formula (I) +
tribenuron,
compound of formula (I) + tribenuron-methyl, compound of formula (I) +
trifluralin, compound
of formula (I) + trinexapac-ethyl, compound of formula (I) + tritosulfuron,
compound of
formula I + 4-hydroxy-34[2-[(2-methoxyethoxy)methy1]-6-(trifluoromethyl)-3-
pyridinyl]carbonylFbicyclo[3.2.1]oct-3-en-2-one (which is bicyclopyrone, CAS
Reg. No.
.. 352010-68-5), compound of formula (I) + one of the specific herbicidal
compounds disclosed
in WO 2010/059676 (Dow, e.g. as defined in one of the examples therein and/or
e.g. can be
plus cloquintocet-mexyl as safener)
, compound of formula (I) + one of the specific herbicidal compounds disclosed
in
WO 2010/059680 (Dow, e.g. as defined in one of the examples therein and/or
e.g. can be
Date Recue/Date Received 2020-05-25

- 115 -
plus cloquintocet-mexyl or another safener)
, compound of formula I + halauxifen (which is 4-amino-3-chloro-6-(4-chloro-2-
fluoro-3-methoxyphenyl)pyridine-2-carboxylic acid, CAS Reg. No. 943832-60-8),
compound
of formula I + halauxifen-methyl (which is methyl 4-amino-3-chloro-6-(4-chloro-
2-fluoro-3-
methoxyphenyl)pyridine-2-carboxylate, CAS Reg. No. 943831-98-9), compound of
formula I
+ iofensulfuron (which is 1-(2-iodophenylsulfonyI)-3-(4-methoxy-6-methyl-1,3,5-
triazin-2-
yl)urea, CAS Reg. No. 1144097-22-2), or compound of formula I + iofensulfuron-
sodium
(which is sodium N-(2-iodophenylsulfonyI)-N'-(4-methoxy-6-methyl-1,3,5-triazin-
2-
yl)carbamimidate, CAS Reg. No. 1144097-30-2);
.. wherein the mixture partners for the compound of formula (I) may optionally
be in the form of
an ester (in particular an agrochemically acceptable ester) or a salt (in
particular an
agrochemically acceptable salt) thereof (e.g. where chemically possible).
For applications in rice, the following mixtures are preferred: compound of
formula (I) +
azimsulfuron, compound of formula (I) + bensulfuron, compound of formula (I) +
bensulfuron-
methyl, compound of formula (I) + benzobicyclon, compound of formula (I) +
benzofenap,
compound of formula (I) + bispyribac, compound of formula (I) + bispyribac-
sodium,
compound of formula (I) + butachlor, compound of formula (I) + cafenstrole,
compound of
formula (I) + cinosulfuron, compound of formula (I) + clomazone, compound of
formula (I) +
clomeprop, compound of formula (I) + cyclosulfamuron, compound of formula (I)
+ cyhalofop,
compound of formula (I) + cyhalofop-butyl, compound of formula (I) + 2,4-D,
compound of
formula (I) + 2,4-D-dimethylammonium, compound of formula (I) + 2,4-D-2-
ethylhexyl,
compound of formula (I) + a choline salt of 2,4-D (see e.g. Examples 2 and 3
of
W02010/123871A1), compound of formula (I) + daimuron, compound of formula (I)
+
dicamba, compound of formula (I) + dicamba-dimethylammonium, compound of
formula (I) +
dicamba-potassium, compound of formula (I) + dicamba-sodium, compound of
formula (I) +
dicamba-diglycolamine, compound of formula (I) + a N,N-
bisjaminopropyl]methylamine salt
of dicamba (see e.g. US2012/0184434A1), compound of formula (I) + diquat,
compound of
formula (I) + diquat dibromide, compound of formula (I) + esprocarb, compound
of formula (I)
+ ethoxysulfuron, compound of formula (I) + fenoxaprop, compound of formula
(I) +
fenoxaprop-ethyl, compound of formula (I) + fenoxaprop-P, compound of formula
(I) +
fenoxaprop-P-ethyl, compound of formula I + fenoxasulfone (CAS Reg. No. 639826-
16-7),
compound of formula (I) + fentrazamide, compound of formula (I) + florasulam,
compound of
formula (I) + glufosinate-ammonium, compound of formula (I) + glyphosate,
compound of
Date Recue/Date Received 2020-05-25

- 116 -
formula (1) + glyphosate-diammonium, compound of formula (1) + glyphosate-
isopropylammonium, compound of formula (1) + glyphosate-potassium, compound of
formula
(1) + halosulfuron, compound of formula (1) + halosulfuron-methyl, compound of
formula (1) +
imazosulfuron, compound of formula 1 + ipfencarbazone (CAS Reg. No. 212201-70-
2),
compound of formula (1) + MCPA, compound of formula (1) + mefenacet, compound
of
formula (1) + mesotrione, compound of formula (1) + metamifop, compound of
formula! +
metazosulfuron (NC-620, CAS Reg. No. 868680-84-6), compound of formula (1) +
metsulfuron, compound of formula (1) + metsulfuron-methyl, compound of formula
(I) + n-
methyl glyphosate, compound of formula (1) + orthosulfamuron, compound of
formula (1) +
oryzalin, compound of formula (1) + oxadiargyl, compound of formula (1) +
oxadiazon,
compound of formula (1) + paraquat dichloride, compound of formula (1) +
pendimethalin,
compound of formula (1) + penoxsulam, compound of formula (1) + pretilachlor,
compound of
formula (1) + profoxydim, compound of formula (1) + propanil, compound of
formula! +
propyrisulfuron (TH-547, CAS Reg. No. 570415-88-2), compound of formula (l)+
pyrazolynate, compound of formula (1) + pyrazosulfuron, compound of formula
(I) +
pyrazosulfuron-ethyl, compound of formula (1) + pyrazoxyfen, compound of
formula (1) +
pyribenzoxim, compound of formula (I) + pyriftalid, compound of formula (I) +
pyriminobac,
compound of formula (1) + pyriminobac-methyl, compound of formula (I) +
pyrimisulfan,
compound of formula (1) + quinclorac, compound of formula (I) + tefuryltrione,
compound of
formula (1) + triasulfuron and compound of formula (1) + trinexapac-ethyl,
compound of
formula (1) + 4-(4'-chloro-4-cyclopropy1-2'-fluorobipheny1-3-y1)-2,2,6,6-
tetramethyl-2H-pyran-
3,5(4H,6H)-dione (which is the compound of Example P8 disclosed on pages 31-32
and 35-
36 of WO 2010/136431 A9 (Syngenta Limited), and which is also compound A-13
disclosed
in pages 4, 5, 7 and 11 of WO 2011/073616 A2 (Syngenta Limited),
compound of formula (I) + 4-(2',4'-
dichloro-4-cyclopropylbipheny1-3-y1)-2,2,6,6-tetramethyl-2H-pyran-3,5(4H,6H)-
dione (which is
the compound of Example P9 disclosed on pages 36-37 and 40-41 of WO
2010/136431 A9
(Syngenta Limited), and which is also compound A-12 disclosed in page 10 of WO
2011/073616A2 (Syngenta Limited),
compound of formula (1) + 4-(4'-chloro-4-ethy1-2.-fluorobiphenyl-3-y1)-
2,2,6,6-tetramethyl-2H-pyran-3,5(4H,6H)-dione (which is compound A-66
disclosed on page
95 of WO 2008/071405 Al (Syngenta Participations AG and Syngenta Limited), and
which is
also compound A-4 disclosed on page 7 of WO 2011/073615 A2 (Syngenta Limited),
compound of formula (I)
Date Recue/Date Received 2020-05-25

-117-
+ 4-(2',4'-dichloro-4-ethylbipheny1-3-y1)-2,2,6,6-tetramethy1-2H-pyran-
3,5(4H,6H)-dione
(which is compound A-45 disclosed on page 93 of WO 2008/071405 Al (Syngenta
Participations AG and Syngenta Limited), and which is also the compound of
Example P10
disclosed on pages 41 and 45 of WO 2010/136431 A9 (Syngenta Limited), and
which is also
.. compound A-7 disclosed on page 7 of WO 2011/073615 A2 (Syngenta Limited),
compound of formula (1) + 4-
(2',4'-dichloro-4-ethylbipheny1-3-y1)-5-(methoxycarbonyloxy)-2,2,6,6-
tetramethy1-2H-pyran-
3(6H)-one (which is compound D-26 disclosed on page 231 of WO 2008/071405 Al
(Syngenta Participations AG and Syngenta Limited), and which is also compound
A-9
disclosed on page 8 of WO 2011/073615 A2 (Syngenta Limited),
compound of formula (1) + one of the
specific herbicidal compounds disclosed in WO 2010/059671 (Dow, e.g. as
defined in one of
the examples therein and/or e.g. can be plus a safener)
, compound of formula 1+ halauxifen (which is 4-amino-3-
chloro-6-(4-chloro-2-fluoro-3-methoxyphenyOpyridine-2-carboxylic acid, CAS
Reg. No.
943832-60-8), compound of formula! + halauxifen-methyl (which is methyl 4-
amino-3-chloro-
6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylate, CAS Reg. No.
943831-98-9),
compound of formula I + iofensulfuron (which is 1-(2-iodophenylsulfony1)-3-(4-
methoxy-6-
methyl-1,3,5-triazin-2-yl)urea, CAS Reg. No. 1144097-22-2), compound of
formula! +
iofensulfuron-sodium (which is sodium N-(2-iodophenylsulfony1)-N'-(4-methoxy-6-
methyl-
1,3,5-triazin-2-yl)carbamimidate, CAS Reg. No. 1144097-30-2), or compound of
formula 1+
triafamone (which is N42-[(4,6-dimethoxy-1,3,5-triazin-2-yl)carbony1]-6-
fluoropheny1]-N-
methy1-1,1-difluoromethanesulfonamide, CAS Reg. No. 874195-61-6);
wherein the mixture partners for the compound of formula (1) may optionally be
in the form of
an ester (in particular an agrochemically acceptable ester) or a salt (in
particular an
agrochemically acceptable salt) thereof (e.g. where chemically possible).
For applications in rice, more preferred is a mixture comprising: a compound
of formula (1) +
azimsulfuron, compound of formula (1) + bensulfuron, compound of formula (1) +
bensulfuron-
methyl, compound of formula (1) + benzobicyclon, compound of formula (1) +
benzofenap,
compound of formula (1) + bispyribac, compound of formula (I) + bispyribac-
sodium,
compound of formula (1) + clomazone, compound of formula (1) + clomeprop,
compound of
formula (1) + cyhalofop, compound of formula (1) + cyhalofop-butyl, compound
of formula (1) +
2,4-D, compound of formula (I) + 2,4-D-dimethylammonium, compound of formula
(1) +
Date Recue/Date Received 2020-05-25

- 118 -2,4-D-2-ethylhexyl, compound of formula (1) + a choline salt of 2,4-0
(see e.g. Examples 2
and 3 of W02010/123871A1), compound of formula (I) + daimuron, compound of
formula (1)
+ dicamba, compound of formula (1) + dicamba-dimethylammonium, compound of
formula (1)
+ dicamba-potassium, compound of formula (1) + dicamba-sodium, compound of
formula (1) +
dicamba-diglycolamine, compound of formula (1) + a N,N-
bisjaminopropylynethylamine salt
of dicamba (see e.g. US2012/0184434A1), compound of formula (1) + esprocarb,
compound
of formula (1) + ethoxysulfuron, compound of formula (I) + fenoxaprop-P,
compound of
formula (1) + fenoxaprop-P-ethyl, compound of formula! + fenoxasulfone (CAS
Reg. No.
639826-16-7), compound of formula (1) + fentrazamide, compound of formula (1)
+
.. florasulam, compound of formula (1) + halosulfuron, compound of formula (I)
+ halosulfuron-
methyl, compound of formula (I) + imazosulfuron, compound of formula I +
ipfencarbazone
(CAS Reg. No. 212201-70-2), compound of formula (1) + MCPA, compound of
formula (1) +
mefenacet, compound of formula (1) + mesotrione, compound of formula I +
metazosulfuron
(NC-620, CAS Reg. No. 868680-84-6), compound of formula (1) + metsulfuron,
compound of
formula (1) + metsulfuron-methyl, compound of formula (1) + orthosulfamuron,
compound of
formula (1) + oxadiargyl, compound of formula (1) + oxadiazon, compound of
formula (I) +
pendimethalin, compound of formula (1) + penoxsulam, compound of formula (1) +
pretilachlor, compound of formula 1+ propyrisulfuron (TH-547, CAS Reg. No.
570415-88-2),
compound of formula (1) + pyrazolynate, compound of formula (1) +
pyrazosulfuron,
compound of formula (1) + pyrazosulfuron-ethyl, compound of formula (I) +
pyrazoxyfen,
compound of formula (1) + pyribenzoxim, compound of formula (1) + pyriftalid,
compound of
formula (1) + pyriminobac, compound of formula (I) + pyriminobac-methyl,
compound of
formula (1) + pyrimisulfan, compound of formula (1) + quinclorac, compound of
formula (1) +
tefuryltrione, compound of formula (1) + triasulfuron and compound of formula
(1) +
trinexapac-ethyl, compound of formula (1) + 4-(4'-chloro-4-cyclopropy1-2'-
fluorobipheny1-3-y1)-
2,2,6,6-tetramethy1-2H-pyran-3,5(4H,6H)-dione (which is the compound of
Example P8
disclosed on pages 31-32 and 35-36 of WO 2010/136431 A9 (Syngenta Limited),
and which
is also compound A-13 disclosed in pages 4, 5, 7 and 11 of WO 2011/073616 A2
(Syngenta
Limited),
compound of formula (1) + 4-(2',4'-dichloro-4-cyclopropylbipheny1-3-y1)-
2,2,6,6-tetramethyl-
2H-pyran-3,5(4H,6H)-dione (which is the compound of Example P9 disclosed on
pages 36-
37 and 40-41 of WO 2010/136431 A9 (Syngenta Limited), and which is also
compound A-12
disclosed in page 10 of WO 2011/073616 A2 (Syngenta Limited),
compound of formula (1) + 4-(4'-chloro-
Date Recue/Date Received 2020-05-25

- 119 -4-ethy1-2'-fluorobipheny1-3-y1)-2,2,6,6-tetramethyl-2H-pyran-3,5(4H,6H)-
dione (which is
compound A-66 disclosed on page 95 of WO 2008/071405 Al (Syngenta
Participations AG
and Syngenta Limited), and which is also compound A-4 disclosed on page 7 of
WO
2011/073615 A2 (Syngenta Limited),
compound of formula (1) + 4-(2',4'-dichloro-4-ethylbipheny1-3-y1)-2,2,6,6-
tetramethy1-2H-pyran-3,5(4H,6H)-dione (which is compound A-45 disclosed on
page 93 of
WO 2008/071405 Al (Syngenta Participations AG and Syngenta Limited), and which
is also
the compound of Example P10 disclosed on pages 41 and 45 of WO 2010/136431 A9
(Syngenta Limited), and which is also compound A-7 disclosed on page 7 of WO
2011/073615 A2 (Syngenta Limited),
compound of formula (1) + 4-(2',4'-dichloro-4-ethylbipheny1-3-y1)-5-
(methoxycarbonyloxy)-2,2,6,6-tetramethy1-2H-pyran-3(6H)-one (which is compound
D-26
disclosed on page 231 of WO 2008/071405 Al (Syngenta Participations AG and
Syngenta
Limited), and which is also compound A-9 disclosed on page 8 of WO 2011/073615
A2
(Syngenta Limited),
compound of formula (1) + one of the specific herbicidal compounds disclosed
in
WO 2010/059671 (Dow, e.g. as defined in one of the examples therein and/or
e.g. can be
plus a safener) , compound of
formula 1+ halauxifen (which is 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-
methoxyphenyl)pyridine-2-carboxylic acid, CAS Reg. No. 943832-60-8), compound
of
formula 1+ halauxifen-methyl (which is methyl 4-amino-3-chloro-6-(4-chloro-2-
fluoro-3-
methoxyphenyl)pyridine-2-carboxylate, CAS Reg. No. 943831-98-9), compound of
formula!
+ iofensulfuron (which is 1-(2-iodophenylsulfony1)-3-(4-methoxy-6-methyl-1,3,5-
triazin-2-
yl)urea, CAS Reg. No. 1144097-22-2), compound of formula! + iofensulfuron-
sodium (which
is sodium N-(2-iodophenylsulfony1)-NL(4-methoxy-6-methyl-1,3,5-triazin-2-
yl)carbamimidate,
CAS Reg. No. 1144097-30-2), or compound of formula 1 + triafamone (which is N-
[2-[(4,6-
dimethoxy-1,3,5-triazin-2-yl)carbony1]-6-fluorophenyl]-N-methyl-1,1-
difluoromethanesulfonamide, CAS Reg. No. 874195-61-6);
wherein the mixture partners for the compound of formula (1) may optionally be
in the form of
an ester (in particular an agrochemically acceptable ester) or a salt (in
particular an
agrochemically acceptable salt) thereof (e.g. where chemically possible).
For applications in soybean, the following mixtures are preferred:
Date Recue/Date Received 2020-05-25

CA 02892076 2015-05-20
WO 2014/096289 PCT/EP2013/077541
- 120 -
compound of formula (I) + acifluorfen, compound of formula (I) + acifluorfen-
sodium,
compound of formula (I) + ametryn, compound of formula (I) + atrazine,
compound of formula
(I) + bentazone, compound of formula (I) + bicyclopyrone, compound of formula
(I) +
bromoxynil, compound of formula (I) + bromoxynil heptanoate, compound of
formula (I) +
bromoxynil octanoate, compound of formula (I) + bromoxynil heptanoate +
bromoxynil
octanoate, compound of formula (I) + carfentrazone, compound of formula (I) +
carfentrazone-ethyl, compound of formula (I) + chloransulam, compound of
formula (I) +
chloransulam-methyl, compound of formula (I) + chlorimuron, compound of
formula (I) +
chlorimuron-ethyl, compound of formula (I) + clethodim, compound of formula
(I) +
clomazone, compound of formula (I) + cyanazine, compound of formula (I) + 2,4-
0
(especially for applications to 2,4-0-tolerant soybean, e.g. genetically-
modified), compound
of formula (I) + 2,4-D-dimethylammonium (especially for applications to 2,4-0-
tolerant
soybean, e.g. genetically-modified), compound of formula (I) + 2,4-D-2-
ethylhexyl (especially
for applications to 2,4-D-tolerant soybean, e.g. genetically-modified),
compound of formula (I)
+ a choline salt of 2,4-D (see e.g. Examples 2 and 3 of W02010/123871A1)
(especially for
applications to 2,4-D-tolerant soybean, e.g. genetically-modified), compound
of formula (I) +
2,4-0 + glyphosate (especially for applications to 2,4-D-tolerant and/or
glyphosate-tolerant
soybean, e.g. genetically-modified), compound of formula (I) + 2,4-D-
dimethylammonium +
glyphosate (especially for applications to 2,4-0-tolerant and/or glyphosate-
tolerant soybean,
e.g. genetically-modified), compound of formula (I) + 2,4-D-2-ethylhexyl +
glyphosate
(especially for applications to 2,4-0-tolerant and/or glyphosate-tolerant
soybean, e.g.
genetically-modified), compound of formula I + a choline salt of 2,4-0 +
glyphosate (see e.g.
Examples 2 and 3 of W02010/123871A1) (especially for applications to dicamba-
tolerant
and/or glyphosate-tolerant soybean, e.g. genetically-modified), compound of
formula (I) +
dicamba (especially for applications to dicamba-tolerant soybean, e.g.
genetically-modified),
compound of formula (I) + dicamba-dimethylammonium (especially for
applications to
dicamba-tolerant soybean, e.g. genetically-modified), compound of formula (I)
+ dicamba-
potassium (especially for applications to dicamba-tolerant soybean, e.g.
genetically-
modified), compound of formula (I) + dicamba-sodium (especially for
applications to
dicamba-tolerant soybean, e.g. genetically-modified), compound of formula (I)
+ dicamba-
diglycolamine (especially for applications to dicamba-tolerant soybean, e.g.
genetically-
modified), compound of formula (I) + a N,N-bis-[aminopropyl]methylamine salt
of dicamba
(see e.g. US2012/0184434A1) (especially for applications to dicamba-tolerant
soybean, e.g.
genetically-modified), compound of formula (I) + dicamba + glyphosate
(especially for

CA 02892076 2015-05-20
WO 2014/096289 PCT/EP2013/077541
- 121 -
applications to dicamba-tolerant and/or glyphosate-tolerant soybean, e.g.
genetically-
modified), compound of formula (I) + dicamba-dimethylammonium + glyphosate
(especially
for applications to dicamba-tolerant and/or glyphosate-tolerant soybean, e.g.
genetically-
modified), compound of formula (I) + dicamba-potassium + glyphosate
(especially for
applications to dicamba-tolerant and/or glyphosate-tolerant soybean, e.g.
genetically-
modified), compound of formula (I) + dicamba-sodium + glyphosate (especially
for
applications to dicamba-tolerant and/or glyphosate-tolerant soybean, e.g.
genetically-
modified), compound of formula (I) + dicamba-diglycolamine + glyphosate
(especially for
applications to dicamba-tolerant and/or glyphosate-tolerant soybean, e.g.
genetically-
.. modified), compound of formula (I) + a N,N-bisqaminopropyl]methylamine salt
of dicamba +
glyphosate (especially for applications to dicamba-tolerant and/or glyphosate-
tolerant
soybean, e.g. genetically-modified), compound of formula (I) + diclosulam,
compound of
formula (I) + dimethenamid, compound of formula (I) + dimethenamid-P, compound
of
formula (I) + diquat, compound of formula (I) + diquat dibromide, compound of
formula (I) +
diuron, compound of formula (I) + fenoxaprop, compound of formula (I) +
fenoxaprop-ethyl,
compound of formula (I) + fenoxaprop-P, compound of formula (I) + fenoxaprop-P-
ethyl,
compound of formula (I) + fluazifop, compound of formula (I) + fluazifop-
butyl, compound of
formula (I) + fluazifop-P, compound of formula (I) + fluazifop-P-butyl,
compound of formula (I)
+ flufenacet, compound of formula (I) + flumetsulam, compound of formula (I) +
flumioxazin,
compound of formula (I) + fluthiacet, compound of formula (I) + fluthiacet-
methyl, compound
of formula (I) + fomesafen, compound of formula (I) + glufosinate, compound of
formula (I) +
glufosinate-ammonium, compound of formula (I) + glyphosate, compound of
formula (I) +
glyphosate-diammonium, compound of formula (I) + glyphosate-isopropylammonium,
compound of formula (I) + glyphosate-potassium, compound of formula (I) +
imazethapyr,
compound of formula (I) + lactofen, compound of formula (I) + mesotrione,
compound of
formula (I) + metolachlor, compound of formula (I) + S-metolachlor, compound
of formula (I)
+ metribuzin, compound of formula (I) + oxyfluorfen, compound of formula (I) +
paraquat,
compound of formula (I) + paraquat dichloride, compound of formula (I) +
pendimethalin,
compound of formula (I) + pyroxasulfone, compound of formula I + quizalofop,
compound of
formula I + quizalofop-ethyl, compound of formula I + quizalofop-P, compound
of formula I +
quizalofop-P-ethyl, compound of formula I + quizalofop-P-tefuryl, compound of
formula (I) +
saflufenacil, compound of formula (I) + sethoxydim, compound of formula (I) +
sulfentrazone,
compound of formula (I) + thifensulfuron, compound of formula (I) +
thifensulfuron-methyl,
compound of formula (I) + tribenuron, compound of formula (I) + tribenuron-
methyl,

- 122 -
compound of formula (I) + trifluralin, compound of formula (I) + 4-(4'-chloro-
4-cyclopropy1-2'-
fluorobipheny1-3-y1)-2,2,6,6-tetramethyl-2H-pyran-3,5(4H,61-0-dione (which is
the compound
of Example P8 disclosed on pages 31-32 and 35-36 of WO 2010/136431 A9
(Syngenta
Limited), and which is also compound A-13 disclosed in pages 4, 5, 7 and 11 of
WO
.. 2011/073616A2 (Syngenta Limited),
compound of formula (I) + 4-(2',4'-dichloro-4-cyclopropylbipheny1-3-y1)-
2,2,6,6-tetramethy1-2H-pyran-3,5(4H,6H)-dione (which is the compound of
Example P9
disclosed on pages 36-37 and 40-41 of WO 2010/136431 A9 (Syngenta Limited),
and which
is also compound A-12 disclosed in page 10 of WO 2011/073616 A2 (Syngenta
Limited),
compound of
formula (I) + 4-(4'-chloro-4-ethy1-2'-fluorobipheny1-3-y1)-2,2,6,6-tetramethyl-
2H-pyran-
3,5(41-1,61-0-dione (which is compound A-66 disclosed on page 95 of WO
2008/071405 Al
(Syngenta Participations AG and Syngenta Limited), and which is also compound
A-4
disclosed on page 7 of WO 2011/073615 A2 (Syngenta Limited),
compound of formula (I) + 4-(2',4'-
dichloro-4-ethylbipheny1-3-y1)-2,2,6,6-tetramethy1-2H-pyran-3,5(4H,6H)-dione
(which is
compound A-45 disclosed on page 93 of WO 2008/071405 Al (Syngenta
Participations AG
and Syngenta Limited), and which is also the compound of Example P10 disclosed
on pages
41 and 45 of WO 2010/136431 A9 (Syngenta Limited), and which is also compound
A-7
disclosed on page 7 of WO 2011/073615 A2 (Syngenta Limited),
or compound of formula (I) + 4-(2',4'-
dichloro-4-ethylbipheny1-3-y1)-5-(methoxycarbonyloxy)-2,2,6,6-tetramethy1-2H-
pyran-3(6H)-
one (which is compound D-26 disclosed on page 231 of WO 2008/071405 Al
(Syngenta
Participations AG and Syngenta Limited), and which is also compound A-9
disclosed on
page 8 of WO 2011/073615 A2 (Syngenta Limited);
wherein the mixture partners for the compound of formula (1) may optionally be
in the form of
an ester (in particular an agrochemically acceptable ester) or a salt (in
particular an
agrochemically acceptable salt) thereof (e.g. where chemically possible).
In the above-mentioned compositions or mixtures comprising a compound of
formula (1) (in
particular, one of the specific compounds disclosed herein, e.g. any of
compounds A-1 to
A-18 or A-19 to A-41 or P-3 to P-7 and/or any of the compounds disclosed in
Tables 1 to 25
Date Recue/Date Received 2020-05-25

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or 26 or 27 herein, present either as a free compound and/or as an
agrochemically
acceptable salt thereof) and one or more further herbicides, the weight ratio
of the compound
of formula (I) to each further herbicide can vary over a large range and is,
typically, from
300:1 to 1:500, especially from 150:1 to 1:200, more especially from 100:1 to
1:100, even
more especially from 30:1 to 1:30. Typically, these weight ratios are measured
as the free
compound(s), i.e. excluding the weight of any associated salt counterion(s).
The compounds of formula I according to the invention can also be used in
combination with
a safener. Preferably, in these mixtures, the compound of the formula I is one
of those
compounds listed (disclosed) in Tables 1 to 25 or 26 or 27 and/or one of the
exemplified
compounds (e.g. A-1 to A-18, or A-19 to A-41, or P-3 to P-7) below. The
following mixtures
with safeners, especially, come into consideration:
compound of formula I + cloquintocet-mexyl, compound of formula I +
cloquintocet acid or an
agrochemically acceptable salt thereof, compound of formula I + fenchlorazole-
ethyl,
compound of formula I + fenchlorazole acid or an agrochemically acceptable
salt thereof,
compound of formula I + mefenpyr-diethyl, compound of formula I + mefenpyr
diacid,
compound of formula I + isoxadifen-ethyl, compound of formula I + isoxadifen
acid,
compound of formula I + furilazole, compound of formula I + furilazole R
isomer, compound
of formula (I) + N-(2-methoxybenzoyI)-4-
[(methylaminocarbonyl)amino]benzenesulfonamide,
compound of formula I + benoxacor, compound of formula I + dichlormid,
compound of
formula I + AD-67, compound of formula I + oxabetrinil, compound of formula I
+ cyometrinil,
compound of formula I + cyometrinil Z-isomer, compound of formula I +
fenclorim, compound
of formula I + cyprosulfamide, compound of formula I + naphthalic anhydride,
compound of
formula I + flurazole, compound of formula I + CL 304,415, compound of formula
I +
dicyclonon, compound of formula I + fluxofenim, compound of formula I + DKA-
24,
compound of formula I + R-29148 and compound of formula I + PPG-1292.
The above-mentioned safeners and herbicides are described, for example, in the
Pesticide
Manual, 14th Edition, British Crop Protection Council, 2006; or The Pesticide
Manual, 15th
edition, 2009, ed. C.D.S. Tomlin, British Crop Production Council. R-29148 is
described, for
example by P.B. Goldsbrough et al., Plant Physiology, (2002), Vol. 130 pp.
1497-1505 and

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references therein. PPG-1292 is known from WO 2009/211761. N-(2-
methoxybenzoyI)-4-
[(methylaminocarbonyl)amino]benzenesulfonamide is known from EP365484.
Especially preferably, in a composition or mixture comprising a compound of
formula (I) (in
particular, one of the specific compounds disclosed herein, e.g. any of
compounds A-1 to
A-18 or A-19 to A-41 or P-3 to P-7 and/or any of the compounds disclosed in
Tables 1 to 25
or 26 or 27 herein, present either as a free compound and/or as an
agrochemically
acceptable salt thereof) and a safener, the safener comprises (e.g. is)
benoxacor,
cloquintocet-mexyl, cloquintocet acid or an agrochemically acceptable salt
thereof,
cyprosulfamide, mefenpyr-diethyl, isoxadifen-ethyl and/or N-(2-methoxybenzoy1)-
4-
Rmethylaminocarbonyl)aminoFbenzenesulfonamide. In one particular embodiment,
the
safener comprises (e.g. is) cloquintocet-mexyl, cloquintocet acid or an
agrochemically
acceptable salt thereof, mefenpyr-diethyl and/or isoxadifen-ethyl; in
particular for use on non-
oat cereals such as wheat, barley, rye and/or triticale. Cloquintocet¨mexyl is
particularly
valuable and is the most preferred safener, especially for use on non-oat
cereals such as
wheat, barley, rye and/or triticale.
In the above-mentioned compositions or mixtures comprising a compound of
formula (I) (in
particular, one of the specific compounds disclosed herein, e.g. any of
compounds A-1 to
A-18 or A-19 to A-41 or P-3 to P-7 and/or any of the compounds disclosed in
Tables 1 to 25
or 26 or 27 herein, present either as a free compound and/or as an
agrochemically
acceptable salt thereof) with a safener, the weight ratio of the compound of
formula (I) to the
safener can vary over a large range and is, typically, from 200:1 to 1:200,
especially from
50:1 to 1:50 such as from 50:1 to 1:20, more especially from 20:1 to 1:20,
even more
.. especially from 20:1 to 1:10. Preferably, the safener comprises (e.g. is)
benoxacor,
cloquintocet-mexyl, cloquintocet acid or an agrochemically acceptable salt
thereof,
cyprosulfamide, mefenpyr-diethyl, isoxadifen-ethyl and/or N-(2-methoxybenzoy1)-
4-
Rmethylaminocarbonyl)aminoFbenzenesulfonamide, and the weight ratio of the
compound of
formula (I) to the safener is from 50:1 to 1:20 or from 20:1 to 1:10, more
preferably from 15:1
.. to 1:2. Typically, these weight ratios are measured as the free
compound(s), i.e. excluding
the weight of any associated salt counterion(s).
Application rates of herbicide (e.g. compound of formula (I)) and/or safener:
The rate of
application of safener relative to the compound of formula (I) is largely
dependent upon the

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mode of application. In the case of field and/or soil and/or plant treatment
(e.g. in a field or
glasshouse): for example from 0.5 to 1000 g of safener per ha, or preferably
from 1 to 250 g
or from 2 to 200 g of safener per ha, are applied; and/or generally from 1 to
2000 g of
compound of formula (I) per ha, or preferably from 5 to 500 g or from 10 to
400 g of
compound of formula (I) per ha, are applied. ha = hectare. Typically, these
application rates
are measured as the free compound, i.e. excluding the weight of any associated
salt
counterion(s). In field treatment, the application of the compound of formula
(I) is preferably
post-emergence.
The compounds and/or herbicidal compositions according to the invention are
suitable for all
methods of application customary in agriculture, such as, for example, pre-
emergence
application, post-emergence application and seed dressing. Post-emergence
application is
preferred. Depending upon the intended use, the safeners can be used for
pretreating the
seed material of the crop plant (dressing the seed or seedlings) or introduced
into the soil
before or after sowing, followed by the application of the (unsafened)
compound of the
formula (I), optionally in combination with a co-herbicide. It can, however,
also be applied
alone or together with the herbicide before or after emergence of the plants.
The treatment of
the plants or the seed material with the safener can therefore take place in
principle
independently of the time of application of the herbicide. The treatment of
the plant by
simultaneous application of herbicide and safener (e.g. in the form of a tank
mixture) is
generally preferred. The rate of application of safener relative to herbicide
is largely
dependent upon the mode of application. In the case of field and/or soil
and/or plant
treatment (e.g. in a field or glasshouse), generally from 0.001 to 5.0 kg of
safener/ha,
preferably from 0.001 to 0.5 kg of safener/ha, are applied. In the case of
seed dressing,
generally from 0.001 to 10 g of safener/kg of seed, preferably from 0.05 to 2
g of safener/kg
of seed, are applied. When the safener is applied in liquid form, with seed
soaking, shortly
before sowing, it is advantageous to use safener solutions which contain the
active
ingredient in a concentration of from 1 to 10 000 ppm, preferably from 100 to
1000 ppm.
In the invention, in the case of field and/or soil and/or plant treatment
(e.g. post-emergence
application), generally from 1 to 2000 g of herbicide (in particular compound
of formula (I)) /
ha, but preferably from 5 to 1000 g of herbicide (in particular compound of
formula (I)) / ha,
more preferably from 10 to 400 g of herbicide (in particular compound of
formula (I)) / ha, is
applied. If a safener is used, in the case of field and/or soil and/or plant
treatment (e.g. post-

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emergence application), generally from 0.5 to 1000 g of safener/ha, preferably
from 2 to
500 g of safener/ha, more preferably from 5 to 200 g of safener/ha, is
applied.
In one particular embodiment, the composition or mixture comprising the
compound of
formula (I) and one or more further herbicides (e.g. as mentioned hereinabove)
can be
applied together with one of the safeners mentioned herein, e.g. hereinabove.
The following Examples illustrate the invention further but do not limit the
invention.

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PREPARATION EXAMPLES
Those skilled in the art will appreciate that certain compounds described
below are 13-
ketoenols, and as such may exist as a single tautomer or as a mixture of keto-
enol and
diketone tautomers, as described, for example by J. March, Advanced Organic
Chemistry,
third edition, John Wiley and Sons. The compounds shown below, and in Table T1
are drawn
as an arbitrary single enol tautomer, but it should be inferred that this
description covers both
the diketone form and any possible enols which could arise through
tautomerism. Where
more than one tautomer is observed in proton NMR, the data shown are for the
mixture of
tautomers. Furthermore, some of the compounds shown below are drawn as single
enantiomers for the purposes of simplicity, but unless specified as single
enantiomers, these
structures should be construed as representing a mixture of enantiomers.
Additionally, some
of the compounds can exist as diastereoisomers, and it should be inferred that
these can be
present as a mixture of diastereoisomers or as any possible single
diastereoisomer. Within
the detailed experimental section the diketone tautomer is chosen for naming
purposes, even
if the predominant tautomer is the enol form.
As used herein, room (ambient) temperature is typically about 15-30 C (e.g.
15-25 C).
Herein, d4 Me0D means tetradeutero-methanol (CD30D).
Example 1: Preparation of 2,2,6,6-Tetramethy1-4-(2-methy1-4-prop-1-
ynylphenyl)pyran-
3,5-dione
OH
===
0
0
Step 1: Preparation of 4-(4-Bromo-2-methylbenzylidene)-2,2,5,5-
tetramethyldihydrofuran-3-
one

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0
0
Br
To an ice-cold solution of 2,2,5,5-tetramethyltetrahydrofuran-3-one (34.2g,
0.24mo1) in
anhydrous 1,2-dimethoxyethane (500m1) is added sodium methoxide (14.0g,
0.26m01) in one
portion. After stirring at 0 C for 5 minutes a second solution of 4-bromo-2-
methylbenzaldehyde (43.6g, 0.22m01) in 1,2-dimethoxyethane (200m1) is added to
the slurry
dropwise over 40 minutes. The reaction mixture is next stirred at 0 C for 2
hours, then diluted
with diethyl ether and washed with 2M hydrochloric acid (x 2). Organic
fractions are
combined, dried over magnesium sulfate, filtered and the filtrate evaporated
in vacuo. The
crude product is then purified by flash column chromatography (5% ethyl
acetate in hexanes
as eluant) to afford 4-(4-bromo-2-methylbenzylidene)-2,2,5,5-
tetramethyldihydrofuran-3-one
as a yellow solid.
Step 2: Preparation of 2-(4-Bromo-2-methylpheny1)-4,4,6,6-
tetramethy1-1,5-
dioxaspiro[2.4]heptan-7-one
0
0
0
Br
To a solution of 4-(4-bromo-2-methylbenzylidene)-2,2,5,5-
tetramethyldihydrofuran-3-one
(52.3g, 0.16mol) in methanol (900 ml) at 35 C is added 50% aqueous hydrogen
peroxide
(16.7g, 0.24m01), followed immediately by a solution of 2M aqueous lithium
hydroxide (16m1,
.. 0.032m01). After stirring at this temperature for 3 hours additional 50%
aqueous hydrogen
peroxide (8.0g, 0.11mol) is added, and the temperature is increased to 60 C.
After heating at
60 C for a further 1 hour the reaction mixture is cooled to room temperature
and 10% sodium
metabisulphite solution (900m1) is added to quench remaining peroxides. The
reaction
mixture is then extracted with both diethyl ether (100m1) and ethyl acetate (2
x 500m1), then
the combined organic phase is washed with saturated sodium bicarbonate then
brine. After
drying over magnesium sulfate the suspension is filtered and the filtrate
evaporated in vacuo
to afford 2-(4-bromo-2-methylpheny1)-4,4,6,6-tetramethy1-1,5-
dioxaspiro[2.4]heptan-7-one as
a yellow solid.
Step 3: Preparation of 4-(4-Bromo-2-methylpheny1)-2,2,6,6-tetramethylpyran-3,5-
dione

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Br
OH
0
0
To an ice-cold solution of concentrated sulphuric acid (500m1) is added a
second solution of
2-(4-bromo-2-methylpheny1)-4,4,6,6-tetramethy1-1,5-dioxaspiro[2.4]heptan-7-one
(40.9g
0.12mol) in dichloromethane (500m1) at 0 C, dropwise over 1 hour. This
biphasic mixture is
stirred vigorously for 2.5 hours at 0 C, then poured into ice-cold water
(500m1) and extracted
with dichloromethane (3 x 500m1). Organic fractions are combined, dried over
magnesium
sulfate, filtered and the filtrate evaporated in vacuo. The crude product is
then purified by
flash column chromatography (5% ethyl acetate in isohexane as eluant) to
afford 4-(4-bromo-
2-methylpheny1)-2,2,6,6-tetramethylpyran-3,5-dione.
Step 4: Preparation of 2,2,6,6-Tetramethy1-4-(2-methy1-4-prop-1-
ynylphenyl)pyran-3,5-dione
OH
0
0
To a mixture of 4-(4-bromo-2-methylpheny1)-2,2,6,6-tetramethylpyran-3,5-dione
(0.200g,
0.59mm01), tetrakis(triphenylphosphine)palladium(0) (0.036g, 0.12mmol) and
tributy1(1-
propynyl) tin (0.54m1, 1.77mm01) is added degassed toluene (4m1), and the
mixture is heated
at 130 C under microwave irradiation for 45mins. The reaction mixture is
quenched with
saturated ammonium chloride, and the crude product is then extracted with
ethyl acetate
(x3). The solution is passed through a bed of diatomaceous earth, and the
combined
organics are washed with brine then dried over magnesium sulfate, filtered,
and the filtrate
concentrated in vacuo. The crude product is then purified by flash column
chromatography
(20% to 100% ethyl acetate in isohexane as eluant) to afford 2,2,6,6-
tetramethy1-4-(2-methyl-
4-prop-1-ynylphenyl)pyran-3,5-dione.

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Example 2 : Preparation of 3-(2-Methyl-4-prop-1-
ynylphenyl)bicyclo[3.2.1]octane-2,4-
dione
OH
0
Step 1: Preparation of 3-(2-Methyl-4-nitrophenyl)bicyclo[3.2.1]octane-2,4-
dione
NO2
OH
0
To a mixture of bicyclo[3.2.1]octane-2,4-dione (1.31g, 9.48mm01),
tris(dibenzylideneacetone)dipalladium(0) (0.550g, 0.60mm01), 2-
dicyclohexylphosphino-
21,41,61-triisopropylbiphenyl (0.430g, 0.90mmo1), powdered potassium phosphate
(3.68g,
17.38mm01) and 2-chloro-5-nitrotoluene (1.36g, 7.92mm01) is added
dimethoxyethane (24
ml), and the reaction mixture is heated at 160 C under microwave irradiation
for 60 minutes.
The mixture is then diluted with ethyl acetate and acidified with 2N aqueous
hydrochloric
acid. This experimental procedure is repeated ten times, and the combined
product is filtered
through a bed of diatomaceous earth (and the residue washed with ethyl acetate
and 2N
aqueous hydrochloric acid). The organic phase is separated and the aqueous
phase is
washed again with ethyl acetate (x3). Organic fractions are combined, washed
with brine,
dried over magnesium sulfate, filtered and the filtrate concentrated in vacuo.
The crude
product is then purified by flash column chromatography (20 to 100% ethyl
acetate in
isohexane as eluant) to afford 3-(2-methyl-4-nitrophenyl)bicyclo[3.2.1]octane-
2,4-dione.
Step 2: Preparation of 3-(4-Amino-2-methylphenyl)bicyclo[3.2.1]octane-2,4-
dione
NH2
OH
0

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To a mixture of 5% palladium on carbon (2.06g, 0.38mmo1, 60% water paste) and
3-(2-
methy1-4-nitrophenyl)bicyclo[3.2.1]octane-2,4-dione (8.64g, 31.63mmo1) is
added ethanol
(79m1) and ethyl acetate (34m1). The reaction mixture is flushed with nitrogen
(x3), then
flushed again with hydrogen (x3) and pressurised to 4 bar. After stirring
under a hydrogen
atmosphere for 8 hours (4 bar pressure, room temperature), the reaction
mixture is then
flushed again with nitrogen (x3), then filtered through a bed of diatomaceous
earth and
washed with ethanol (2L). The crude product is then concentrated in vacuo to
afford 3-(4-
amino-2-methylphenyObicyclo[3.2.1]octane-2,4-dione.
Step 3: Preparation of 3-(4-Bromo-2-methylphenyObicyclo[3.2.1]octane-2,4-dione
Br
OH
0
A solution of 3-(4-amino-2-methylphenyl)bicyclo[3.2.1]octane-2,4-dione (1.00
g, 4.11 mmol)
in ethanol (20 ml) is cooled to 0 C then evacuated, flushed with nitrogen, and
maintained
under a nitrogen atmosphere. Hydrobromic acid (4.9m1, 14.80mmo1, 48% wt. in
water) is
added, followed by the dropwise addition of a solution of sodium nitrite
(0.528g, 6.17mmol) in
distilled water (1.2m1). After stirring at 0 C for 1 hour a second solution of
copper(I) bromide
(0.71g, 4.93mm01) in hydrobromic acid (4.9m1, 14.80mmo1, 48% wt. in water) is
added
dropwise, and the reaction mixture is allowed to warm to room temperature and
stir for an
additional 20 hours. The reaction mixture is poured into ice water then
extracted with ethyl
acetate (x3). The combined organic extracts are washed with brine, dried over
magnesium
sulfate, filtered and the filtrate concentrated in vacuo. The crude product is
then purified by
flash column chromatography (10-100% ethyl acetate in isohexane as eluant) to
afford 3-(4-
bromo-2-methylphenyl)bicyclo[3.2.1]octane-2,4-dione.
Step 4: Preparation of 3-(4-Bromo-2-methylpheny1)-4-methoxybicyclo[3.2.1]oct-3-
en-2-one
B
0
0
r

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To a solution of 3-(4-bromo-2-methylphenyl)bicyclo[3.2.1]octane-2,4-dione
(0.25g,
0.82mm01) in acetone (10m1) is added potassium carbonate (0.17g, 1.23mm01)
followed by
iodomethane (0.26m1, 4.07mm01), and the suspension is stirred at room
temperature for 21
hours. Volatile solvents are removed in vacuo, and the crude product is then
washed with
distilled water and extracted with ethyl acetate (x3). The combined organic
extracts are
washed with brine, dried over magnesium sulfate, filtered and the filtrate
concentrated in
vacuo. Purification by flash column chromatography (20-80% ethyl acetate in
isohexane as
eluant) affords 3-(4-bromo-2-methylpheny1)-4-methoxybicyclo[3.2.1]oct-3-en-2-
one.
Step 5: Preparation of 2-Methoxy-3-(2-methy1-4-prop-1-
ynylphenyObicyclo[3.2.1]oct-2-en-4-
one
0
A mixture of 3-(4-bromo-2-methylpheny1)-4-methoxybicyclo[3.2.1]oct-3-en-2-one
(0.20g,
0.62mm01), copper(1) iodide (0.012g, 0.06mm01), cesium fluoride (0.188g,
1.24mm01), [1,1'-
bis(diphenylphosphino)ferrocene]palladium(11)chloride (0.049g, 0.06mmo1),
tributy1(1-
propenyl) tin (0.57m1, 1.87mm01) and N,N-dimethylformamide (2 ml) is flushed
with nitrogen,
then heated at 110 C under microwave irradiation for 30 minutes. Distilled
water is added to
the reaction mixture and the crude product is extracted with ethyl acetate
(x3). Organic
fractions are combined, washed with brine, dried over magnesium sulfate,
filtered and the
filtrate concentrated in vacuo. Purification by flash column chromatography
(20-80% ethyl
acetate in isohexane as eluant) affords 2-methoxy-3-(2-methy1-4-prop-1-
ynylphenyl)bicyclo[3.2.1]oct-2-en-4-one.
Step 6: Preparation of 3-(2-Methyl-4-prop-1-ynylphenyl)bicyclo[3.2.1]octane-
2,4-dione
OH
0

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A solution of 2-methoxy-3-(2-methy1-4-prop-1-ynylphenyl)bicyclo[3.2.1]oct-2-en-
4-one
(0.150g, 0.54mm01) in a mixture of acetone (2m1) and 2 M hydrochloric acid
(0.5m1,
1.00mmol) is heated at 120 C under microwave irradiation for 10 minutes. The
reaction
mixture is then concentrated in vacuo and partitioned between distilled water
and ethyl
acetate. The aqueous phase is then washed with additional ethyl acetate (x2).
Organic
fractions are combined, washed with brine, dried over magnesium sulfate,
filtered and the
filtrate concentrated in vacuo. Purification by flash column chromatography
(20-80% ethyl
acetate in isohexane as eluant) affords 3-(2-methy1-4-prop-1-
ynylphenyl)bicyclo[3.2.1]octane-
2,4-dione.
Example 3 : Preparation of 3-(2-Chloro-6-ethyl-4-prop-1-
ynylphenyl)bicyclo[3.2.1]octane-2,4-dione
OH
CI
0
Step 1: Preparation of 341-(2-Chloro-6-
ethylphenyl)methylidene]bicyclo[2.2.1]heptan-
2-one
0
CI
To a solution of norcamphor (3.87g, 35.18mmol) and 2-chloro-6-
ethylbenzaldehyde (e.g.
described in W02011/023795) (8.31 g, 49.26 mmol) in ethanol (100m1) is added
solid
potassium hydroxide (0.60g, 10.78mm01). The reaction mixture is then heated at
reflux for
20 hours, then cooled to 0 C followed by the addition of distilled water
(30m1) and 2N
aqueous hydrochloric acid (30m1). The aqueous phase is extracted with ethyl
acetate (x3),
and the combined organic fractions are washed with brine, dried over anhydrous
magnesium
sulfate, filtered and the filtrate concentrated in vacuo. Purification by
flash column
chromatography (5% ethyl acetate in isohexane as eluant) affords 341-(2-chloro-
6-
ethylphenyl)methylidene]bicyclo[2.2.1]heptan-2-one.

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Step 2: Preparation of 4-[1-(2-Chloro-6-ethylphenyl)methylidene]-3-
oxabicyclo[3.2.1]octan-2-
one
0
0
CI
To a solution of 341-(2-chloro-6-ethylphenyl)methylidene]bicyclo[2.2.1]heptan-
2-one (6.80g,
26.08mm01) in tert-butanol (32m1) is added hydrogen peroxide (3.01m1,
44.33mmo1, 50%
aqueous) and selenium dioxide (0.136g, 1.22mm01), and the solution is stirred
at room
temperature for 4 days. To the reaction mixture is then added distilled water
and diethyl
ether, the phases are separated, and the aqueous phase extracted again with
diethyl ether
(x3). The combined organic fractions are washed with distilled water (x8),
then concentrated
in vacuo. The crude product is purified by flash column chromatography (5-25%
ethyl acetate
in isohexanes as eluant) to afford 4-[1-(2-chloro-6-ethylphenyl)methylidene]-3-
oxabicyclo[3.2.1]octan-2-one.
Step 3: Preparation of 3-(2-Chloro-6-ethylphenyl)bicyclo[3.2.1]octane-2,4-
dione
OH
CI
0
To a solution of 4-[1-(2-chloro-6-ethylphenyl)methylidene]-3-
oxabicyclo[3.2.1]octan-2-one
(4.03g, 14.56mmo1) in N,N-dimethylformamide (95m1) at 80 C is added a second
solution of
sodium methoxide (6.29m1, 29.12mmol, 25 wt.% in methanol) dropwise. The
reaction mixture
is stirred at 80 C for 1 hour 55 minutes, then cooled to to 0 C. 2N aqueous
hydrochloric
acid (45m1) and water (45m1) are added and the crude product is extracted with
ethyl acetate
(x3). The combined organic extracts are washed successively with distilled
water (x3) then
brine, and finally dried over magnesium sulfate, filtered and the filtrate
concentrated in vacuo.

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Purification by flash column chromatography (30-100% ethyl acetate in
isohexanes as
eluant) affords 3-(2-chloro-6-ethylphenyl)bicyclo[3.2.1]octane-2,4-dione.
Step 4: Preparation of 3-(2-Chloro-6-ethylpheny1)-4-methoxybicyclo[3.2.1]oct-3-
en-2-one
0
CI
0
To a solution of 3-(2-chloro-6-ethylphenyl)bicyclo[3.2.1]octane-2,4-dione
(2.25g, 8.13mmol)
in acetone (100m1) is added potassium carbonate (1.69g, 12.20mm01) then
iodomethane
(2.53m1, 40.65mm01), and the suspension is stirred at room temperature for 18
hours.
Volatile solvents are removed in vacuo, and the crude product is partitioned
between distilled
water and ethyl acetate. The phases are separated and the aqueous phase is
extracted
again with additional ethyl acetate (x3). Organic fractions are combined,
washed with brine,
dried over anhydrous magnesium sulfate, filtered and the filtrate concentrated
in vacuo.
Purification by flash column chromatography (5-50% ethyl acetate in isohexanes
as eluent)
affords 3-(2-chloro-6-ethylphenyI)-4-methoxybicyclo[3.2.1]oct-3-en-2-one.
Step 5: Preparation of 342-Chloro-6-ethy1-4-(4,4,5,5-
tetramethyl[1,3,2]dioxaborolan-2-
yl)phenyl]-4-methoxybicyclo[3.2.1]oct-3-en-2-one
0
0 0
CI
0
Step 5a:
To a mixture of bis(pinacolato)diboron (2.59g, lOmmol), (1,5-
cyclooctadiene)(methoxy)iridium(1) dimer (0.104g, 0.157mm01) and 4,4`-di-t-
buty1-2,2`-

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bipyridine (0.84g, 0.312mm01) under a nitrogen atmosphere, is added anhydrous
methyl-tert-
butyl ether (25m1), and the solution is shaken for 15 minutes.
Step 5b:
To 3-(2-chloro-6-ethylphenyI)-4-methoxybicyclo[3.2.1]oct-3-en-2-one (0.241g,
0.83mmo1)
under a nitrogen atmosphere is added 2.0m1 of the catalyst solution, prepared
as described
in Step 5a. After stirring at room temperature for 1 minute the reaction
mixture is then heated
at 80 C for 60 minutes under microwave irradiation. After cooling to room
temperature
volatiles are removed in vacuo, and the crude product is purified by flash
column
chromatography (10-100% ethyl acetate in isohexanes as eluant) to afford 3-[2-
chloro-6-
ethy1-4-(4,4,5,5-tetramethyl[1,3,2]dioxaborolan-2-yl)phenyl]-4-
methoxybicyclo[3.2.1]oct-3-en-
2-one.
Step 6: Preparation of 3-(2-Chloro-6-ethy1-4-prop-1-ynylpheny1)-4-
methoxybicyclo[3.2.1]oct-
3-en-2-one
0
CI
0
To a solution of 1-propyn-1-y1 iodide (0.89g, 0.54mm01) in toluene (5m1),
methanol (5m1) and
distilled water (2.5m1) is added 342-chloro-6-ethy1-4-(4,4,5,5-
tetramethyl[1,3,2]dioxaborolan-
2-yOpheny11-4-methoxybicyclo[3.2.1]oct-3-en-2-one (0.204g, 0.49mm01),
palladium(II)
chloride (0.09g, 0.05mm01) and potassium carbonate (135 mg, 0.98 mmol), and
the reaction
mixture is heated at 80 C for 2 hours. The solution is then extracted with
diethyl ether and
the combined organic fractions are washed with distilled water, dried over
anhydrous
magnesium sulfate, filtered and the filtrate concentrated in vacuo.
Purification by flash
column chromatography (10-100% ethyl acetate in isohexanes as eluant) affords
3-(2-chloro-
6-ethy1-4-prop-1-ynylpheny1)-4-methoxybicyclo[3.2.1]oct-3-en-2-one.
Step 7: Preparation of 3-(2-Chloro-6-ethy1-4-prop-1-
ynylphenyl)bicyclo[3.2.1]octane-2,4-
dione

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OH
CI
0
A solution of 3-(2-chloro-6-ethy1-4-prop-1-ynylpheny1)-4-
methoxybicyclo[3.2.1]oct-3-en-2-one
(0.48g, 1.46mmol) in acetone (1m1) and 2N aqueous hydrochloric acid (1m1) is
heated at
120 C under microwave irradiation for 10 minutes. The reaction mixture is then
cooled to
room temperature and partitioned between distilled water and ethyl acetate.
The aqueous
phase is extracted again with ethyl acetate (x3), and the combined organic
fractions are
washed with brine, dried over anhydrous magnesium sulfate, filtered and the
filtrate
concentrated in vacuo to afford 3-(2-chloro-6-ethy1-4-prop-1-ynyl-pheny1)-
.. bicyclo[3.2.1]octane-2,4-dione.
Example 4: Preparation of 3-(4-Chloroethyny1-2,6-
dimethylphenyl)bicyclo[3.2.1]octane-2,4-dione
Ci
OH
0
Step 1: Preparation of 341-(4-Bromo-2,6-
dimethylphenyOmethylideneThicyclo[2.2.1]heptan-2-
one
0 Br
To a solution of norcamphor (1.18g, 10.73mm01) and 4-bromo-2,6-dimethyl-
benzaldehyde
(e.g. described in W02008/021851) (3.43g, 16.10mmol) in ethanol (40m1) is
added solid
potassium hydroxide (0.198g, 3.52mm01). The reaction mixture is then heated at
reflux for
20 hours, cooled to 0 C followed by the addtion of distilled water (15m1) and
2N aqueous

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hydrochloric acid (15m1). The aqueous phase is then extracted with ethyl
acetate (x3), and
the combined organic fractions are washed with brine, dried over anhydrous
magnesium
sulfate, filtered and the filtrate concentrated in vacuo. Purification by
flash column
chromatography (5% ethyl acetate in isohexane as eluant) affords 3-[1-(4-bromo-
2,6-
dimethylphenyl)methylidene]bicyclo[2.2.1]heptan-2-one.
Step 2: Preparation of 4-[1-(4-Bromo-2,6-
dimethylphenyl)methylidene]-3-
oxabicyclo[3.2.1]octan-2-one
0
B
0
r
To a solution of 3-[1-(4-bromo-2,6-
dimethylphenyl)methylidene]bicyclo[2.2.1]heptan-2-one
(6.50g, 21.30mm01) in tert-butanol (26m1) is added hydrogen peroxide (3.46m1,
36.23mmo1,
50% aqueous) and selenium dioxide (0.11g, 1.0mmol), and the solution is
stirred at room
temperature for 4 days. To the reaction mixture is then added distilled water
and diethyl
ether, the phases are separated, and the aqueous phase is extracted again with
diethyl ether
(x3). The combined organic fractions are washed with distilled water (x8),
then concentrated
in vacuo. The crude product is purified by flash column chromatography (5-50%
ethyl acetate
in isohexanes as eluant) to afford 441-(4-bromo-2,6-
dimethylphenyl)methylidene]-3-
oxabicyclo[3.2.1]octan-2-one.
Step 3: Preparation of 3-(4-Bromo-2,6-dimethylphenyl)bicyclo[3.2.1]octane-2,4-
dione
B
OH
0
r
To a solution of 4-[1-(4-bromo-2,6-dimethylphenyl)methylidene]-3-
oxabicyclo[3.2.1]octan-2-
one (3.185g, 9.92mm01) in N,N-dimethylformamide (65m1) at 80 C is added a
second
solution of sodium methoxide (4.29m1, 19.83mmo1, 25 wt.% in methanol)
dropwise. The
reaction mixture is stirred at 80 C for 1 hour 55 minutes, then cooled to to
0 C. 2N aqueous

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hydrochloric acid (30m1) and water (30m1) are added and the crude product is
extracted with
ethyl acetate (x3). The combined organic extracts are washed successively with
distilled
water (x3) then brine, and finally dried over magnesium sulfate, filtered and
the filtrate
concentrated in vacuo. Purification by flash column chromatography (30-100%
ethyl acetate
in isohexanes as eluant) affords 3-(4-bromo-2,6-
dimethylphenyl)bicyclo[3.2.1]octane-2,4-
dione.
Step 4: Preparation of 3-(4-Bromo-2,6-dimethylphenyI)-4-
methoxybicyclo[3.2.1]oct-3-en-2-
one
Br
0
0
To a solution of 3-(4-bromo-2,6-dimethylphenyl)bicyclo[3.2.1]octane-2,4-dione
(0.40g,
1.25mm01) in acetone (20m1) is added potassium carbonate (0.343g, 2.48mm01)
then
iodomethane (0.51m1, 8.25mm01), and the suspension is stirred at room
temperature for 18
hours. Volatile solvents are removed in vacuo, and the crude product is
partitioned between
distilled water and ethyl acetate. The phases are separated and the aqueous
phase is
extracted again with additional ethyl acetate (x3). Organic fractions are
combined, washed
with brine, dried over anhydrous magnesium sulfate, filtered and the filtrate
concentrated in
vacuo. Purification by flash column chromatography (5-90% ethyl acetate in
isohexanes as
eluent) affords 3-(4-bromo-2,6-dimethylpheny1)-4-methoxybicyclo[3.2.1]oct-3-en-
2-one.
Step 5: Preparation of 3-(4-Ethyny1-2,6-dimethylpheny1)-4-
methoxybicyclo[3.2.1]oct-3-en-2-
one
0
0
A mixture of 3-(4-bromo-2,6-dimethylphenyI)-4-methoxybicyclo[3.2.1]oct-3-en-2-
one (0.21g,
0.63mm01), copper(I) iodide (0.012g, 0.06mm01), cesium fluoride (0.197g,
1.30mmo1), [1,1'-

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bis(diphenylphosphino)ferrocene]palladium(11)chloride (0.027g, 0.033mm01),
tributy1(1-
propenyl) tin (0.54m1, 1.87mmol) and N,N-dimethylformamide (3m1) is flushed
with nitrogen,
then heated at 110 C under microwave irradiation for 45 minutes. Distilled
water is added to
the reaction mixture and the crude product is extracted with ethyl acetate
(x3). Organic
fractions are combined, washed with brine, dried over magnesium sulfate,
filtered and the
filtrate concentrated in vacuo. Purification by flash column chromatography (5-
70% ethyl
acetate in isohexane as eluant) affords 3-(4-ethyny1-2,6-dimethylpheny1)-4-
methoxybicyclo[3.2.1]oct-3-en-2-one.
Step 6: Preparation of 3-(4-Chloroethyny1-2,6-dimethylpheny1)-4-
methoxybicyclo[3.2.1]oct-3-
en-2-one
a
0
0
A mixture of 3-(4-bromo-2,6-dimethylpheny1)-4-methoxybicyclo[3.2.1]oct-3-en-2-
one (0.20g,
0.71mmol), N-chlorosuccinimide (0.114g, 0.85mm01) and silver acetate (0.012g,
0.071mmol)
in acetone (5m1) is heated at reflux overnight, then allowed to cool to room
temperature. The
reaction mixture is filtered then concentrated in vacuo. The crude product is
purified by flash
column chromatography (5-60% ethyl acetate in isohexane as eluant) to afford 3-
(4-
chloroethyny1-2,6-dimethylpheny1)-4-methoxybicyclo[3.2.1]oct-3-en-2-one.
Step 7: Preparation of 3-(4-Chloroethyny1-2,6-
dimethylphenyObicyclo[3.2.1]octane-2,4-dione
a
OH
0
A solution of 3-(2-chloro-6-ethy1-4-prop-1-ynylpheny1)-4-
methoxybicyclo[3.2.1]oct-3-en-2-one
(0.170g, 0.54mm01) in acetone (3m1) and 2N aqueous hydrochloric acid (1m1) is
heated at
120 C under microwave irradiation for 10 minutes. The reaction mixture is then
cooled to

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room temperature and partitioned between distilled water and ethyl acetate.
The aqueous
phase is extracted again with ethyl acetate (x3), and the combined organic
fractions are
washed with brine, dried over anhydrous magnesium sulfate, filtered and the
filtrate
concentrated in vacuo. The crude product is purified by flash column
chromatography (5-
70% ethyl acetate in isohexane as eluant) to afford 3-(4-chloroethyny1-2,6-
dimethylphenyl)bicyclo[3.2.1]octane-2,4-dione.
Example 5: Preparation of 2-[4-(2-chloroethyny1)-2,6-dimethylphenyl]-5-
(tetrahydropyran-4-ylmethyl)cyclohexane-1,3-dione
0 H
0
ci
Step 1: Preparation of 2-(4-bromo-2,6-dimethylpheny1)-5-(tetrahydropyran-4-
ylmethyl)cyclohexane-1,3-dione
o H
0
0
Br
To a solution of 5-(tetrahydropyran-4-ylmethyl)cyclohexane-1,3-dione
(0.420g, 2.0mmol) (e.g. reported in W02010/046194) and 4-dimethylaminopyridine
(1.22g,
10.0mmol) in chloroform (20m1) is added 4-bromo-2,6-dimethylphenyllead
triacetate (1.25g,
2.2mm01) (e.g. reported in W02009/074314) and toluene (5m1). The mixture is
stirred under
a nitrogen atmosphere then heated at 80 C for 1.5 hours, followed cooling to
room
temperature. The reaction mixture is acidified with 2N aqueous hydrochloric
acid, stirred
vigorously for 10 minutes then filtered through a bed of diatomaceous earth
and washed with
dichloromethane (40m1). The organic phase was washed with 2N aqueous
hydrochloric acid
then brine, dried over sodium sulphate, filtered and the filtrate concentrated
in vacuo. The
crude product is purified by flash column chromatography (20-100% ethyl
acetate in
isohexane as eluent) to afford 2-(4-bromo-2,6-dimethylphenyI)-5-
(tetrahydropyran-4-
ylmethyl)cyclohexane-1,3-dione.

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Step 2: Preparation of 2-(4-bromo-2,6-dimethylpheny1)-3-methoxy-5-
(tetrahydropyran-4-
ylmethyl)cyclohex-2-en-1-one
o
0
0
Br
To a solution of 2-(4-bromo-2,6-dimethylphenyI)-5-(tetrahydropyran-4-
ylmethyl)cyclohexane-
1,3-dione (0.470g, 1.195mmol) in acetone (20m1) is added potassium carbonate
(0.248g,
1.80mmol) then iodomethane (0.850g, 5.99mm01), and the suspension is stirred
at room
temperature for 16 hours. Volatile solvents are removed in vacuo, and the
crude product is
partitioned between distilled water and ethyl acetate. The phases are
separated and the
aqueous phase is extracted again with additional ethyl acetate (x3). Organic
fractions are
combined, washed with brine, dried over anhydrous magnesium sulfate, filtered
and the
filtrate concentrated in vacuo. Purification by flash column chromatography
(20-70% ethyl
acetate in isohexanes as eluent) affords 2-(4-bromo-2,6-dimethylphenyI)-3-
methoxy-5-
(tetrahydropyran-4-ylmethyl)cyclohex-2-en-1-one.
Step 3: Preparation of 2-(4-ethyny1-2,6-dimethylpheny1)-3-methoxy-5-
(tetrahydropyran-4-
ylmethyl)cyclohex-2-en-1-one
oI
A mixture of 2-(4-bromo-2,6-dimethylphenyI)-3-methoxy-5-(tetrahydropyran-4-
ylmethyl)cyclohex-2-en-1-one (0.203g, 0.50mm01), copper(1) iodide (0.019g,
0.10mmol),
cesium fluoride (0.152g, 1.00mmol),
[1,1'bis(diphenylphosphino)ferrocene]palladium(I1)chloride (0.041g, 0.05mmol),
tributy1(1-
ethynyl) tin (0.550g, 1.74mm01) and N,N-dimethylacetamide (2 ml) is flushed
with nitrogen,
then heated at 110 C under microwave irradiation for 2 hours. Distilled water
is added to the
reaction mixture and the crude product is extracted with ethyl acetate (x3).
Organic fractions
are combined, washed with brine, dried over magnesium sulfate, filtered and
the filtrate

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concentrated in vacuo. Purification by reverse phase HPLC (15-70% acetonitrile
in water as
eluent) affords 2-(4-ethyny1-2,6-dimethylpheny1)-3-methoxy-5-(tetrahydropyran-
4-
ylmethyl)cyclohex-2-en-1-one.
Step 4: Preparation of 244-(2-chloroethyny1)-2,6-dimethylpheny11-3-methoxy-5-
(tetrahydropyran-4-ylmethyl)cyclohex-2-en-1-one
o1
0
cI
To a solution of 2-(4-ethyny1-2,6-dimethylpheny1)-3-methoxy-5-(tetrahydropyran-
4-
ylmethyl)cyclohex-2-en-1-one (0.220g, 0.62mm01) in acetone (5m1) is added N-
chlorosuccinimide (0.100g, 0.75mm01) and silver acetate (0.007g, 0.06mmol).
The mixture is
heated at reflux under a nitrogen atmosphere overnight, then allowed to cool
to room
temperature. The reaction mixture is filtered then concentrated in vacuo. The
crude product
is purified by flash column chromatography (10-100% ethyl acetate in isohexane
as eluent)
to afford 244-(2-chloroethyny1)-2,6-dimethyl-pheny1]-3-methoxy-5-
(tetrahydropyran-4-
ylmethyl)cyclohex-2-en-1-one.
Step 5: Preparation of Preparation of 2-[4-(2-chloroethyny1)-2,6-
dimethylpheny1]-5-
(tetrahydropyran-4-ylmethyl)cyclohexane-1,3-dione
0H
0
0
CI
A solution of 244-(2-chloroethyny1)-2,6-dimethylpheny1]-3-methoxy-5-
(tetrahydropyran-4-
ylmethyl)cyclohex-2-en-1-one (0.030g, 0.078mm01) in acetone (1.5m1) and 2N
aqueous
hydrochloric acid (0.5m1) is heated at 60 C under microwave irradiation for 30
minutes. The
reaction mixture is then cooled to room temperature, concentrated in vacuo and
the crude

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product is partitioned between distilled water and ethyl acetate. The aqueous
phase is
extracted again with ethyl acetate, and the combined organic fractions are
washed with
brine, dried over anhydrous magnesium sulfate, filtered and the filtrate
concentrated in
vacuo. The crude product is purified by flash column chromatography (10-100%
ethyl acetate
in isohexane as eluent) to afford 244-(2-chloroethyny1)-2,6-dimethyl-pheny11-5-
(tetrahydropyran-4-ylmethyl)cyclohexane-1,3-dione.
Example 6: Preparation of 2-(2,6-dimethy1-4-prop-1-ynylpheny1)-5-
(tetrahydropyran-4-
ylmethyl)cyclohexane-1,3-dione
0
0
0
Step 1: 2-(2,6-dimethy1-4-prop-1-ynyl-pheny1)-3-methoxy-5-(tetrahydropyran-4-
ylmethyl)cyclohex-2-en-1-one
0
0
0
A mixture of 2-(4-bromo-2,6-dimethylpheny1)-3-methoxy-5-(tetrahydropyran-4-
ylmethyl)cyclohex-2-en-1-one (0.203g, 0.50mmo1), copper(1) iodide (0.019g,
0.10mmol),
cesium fluoride (0.152g, 1.00mmol),
[1,1'bis(diphenylphosphino)ferrocene]palladium(11)chloride (0.041g, 0.05mmol),
tributy1(1-
propenyl) tin (0.574g, 1.74mmol) and N,N-dimethylacetamide (2 ml) is flushed
with nitrogen,
then heated at 110 C under microwave irradiation for 60 minutes. Distilled
water is added to
the reaction mixture and the crude product is extracted with ethyl acetate
(x3). Organic
fractions are combined, washed with brine, dried over magnesium sulfate,
filtered and the
filtrate concentrated in vacuo. Purification by reverse phase HPLC (15-70%
acetonitrile in
water as eluant) affords 2-(2,6-dimethy1-4-prop-1-ynylpheny1)-3-methoxy-5-
(tetrahydropyran-
4-ylmethyl)cyclohex-2-en-1-one.

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Step 2: Preparation of 2-(2,6-dimethy1-4-prop-1-ynylpheny1)-5-(tetrahydropyran-
4-
ylmethyl)cyclohexane-1,3-dione
0
0
0
A solution of 2-(2,6-dimethy1-4-prop-1-ynylpheny1)-3-methoxy-5-
(tetrahydropyran-4-
ylmethyl)cyclohex-2-en-1-one (0.205g, 0.58mm01) in acetone (6m1) and 2N
aqueous
hydrochloric acid (2m1) is heated at 60 C under microwave irradiation for 30
minutes. The
reaction mixture is then cooled to room temperature, concentrated in vacuo and
the crude
product is partitioned between distilled water and ethyl acetate. The aqueous
phase is
extracted again with ethyl acetate, and the combined organic fractions are
washed with
brine, dried over anhydrous magnesium sulfate, filtered and the filtrate
concentrated in
vacuo. The crude product is purified by flash column chromatography (10-100%
ethyl acetate
in isohexane as eluent) to afford 2-(2,6-dimethy1-4-prop-1-ynylpheny1)-5-
(tetrahydropyran-4-
ylmethyl)cyclohexane-1 ,3-d lone.
Example 7: Preparation 3-(2-chloro-6-methoxy-4-prop-1-ynylphenyl)-
bicyclo[3.2.1]octane-2,4-dione
CI
0
0 C)`
Step 1: Preparation of (3E)-3-[(2-chloro-6-methoxy-phenyl)methylene]norbornan-
2-one

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0
CI
/0
Norboman-2-one (5.00 g, 45.39 mmol) and 2-chloro-6-methoxy-benzaldehyde (10.84
g,
63.55 mmol) was dissolved in ethanol (136 mL). Potassium hydroxide (0.76 g,
13.62 mmol)
was added to the reaction in one portion and refluxed at 85 C under nitrogen
for 19 hours.
The reaction mixture was concentrated to minimum volume. Ethyl acetate (100
mL) was
added followed by 2N aqueous hydrochloric acid (100 mL) dropwise at 0 C. The
mixture
was diluted with ethyl acetate and the phases separated. The aqueous layer was
extracted
twice with ethyl acetate and the combined organics were washed with brine,
dried over
magnesium sulphate, filtered and reduced in vacuo. The crude product was
purified by flash
column chromatography over silica gel (5-30% ethyl acetate in hexanes as
eluant) to afford
(3E)-3-[(2-chloro-6-methoxy-phenyl)methylene]norbornan-2-one as an dark red
oil.
Step 2: Preparation of (2Z)-2-[(2-chloro-6-methoxy-phenyl)methylene]-3-
oxabicyclo[3.2.1]octan-4-one
0
CI
0
(3E)-3-[(2-chloro-6-methoxy-phenyl)methylene]norbornan-2-one (11.93 g, 45.41
mmol) was
stirred in 2-methylpropan-2-ol (59 mL) at room temperature and hydrogen
peroxide (5 mL,
77.19 mmol) was added dropwise to the mixture. Selenium dioxide (0.20 g, 1.82
mmol) was
added to the reaction and stirred at room temperature for 24 hours. Another
portion of
hydrogen peroxide (5 mL, 77.19 mmol) was added dropwise to the reaction and
stirred for an
additional 24 hours. Pentane was added to the reaction mixture and the
precipitate was
.. filtered. The crude solid was washed with additional pentane and air dried
to afford (2Z)-2-

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[(2-chloro-6-methoxy-phenyl)methylene]-3-oxabicyclo[3.2.1]octan-4-one as a
colourless
solid.
Step 3: Preparation of 3-(2-chloro-6-methoxy-phenyl)bicyclo[3.2.1]octane-2,4-
dione
CI
0
0
0
(2Z)-2-[(2-chloro-6-methoxy-phenyl)methylene]-3-oxabicyclo[3.2.1]octan-4-one
(8.74 g, 31.4
mmol) was dissolved in toluene (94 mL). Eaton's reagent (94 mL) was added in
one portion
at room temperature and stirred at 70 C under nitrogen for 1 hour. The
reaction mixture was
quenched onto ice/6M NaOH (300 g:300 mL) and basified until the solution was
pH 14. The
mixture was stirred for 15 minutes and the phases were separated. The aqueous
layer was
extracted with additional ethyl acetate and acidified to pH 1-3 using
concentrated aqueous
hydrochloric acid. The acidic aqueous layer was extracted twice with
dichloromethane, dried
over magnesium sulphate, filtered and reduced in vacuo to afford 3-(2-chloro-6-
methoxy-
phenyl)bicyclo[3.2.1]octane-2,4-dione as a beige solid.
Step 4: Preparation of 3-(2-chloro-6-methoxy-phenyl)-2-methoxy-
bicyclo[3.2.1]oct-2-en-4-one
CI
0
0
0
3-(2-chloro-6-methoxy-phenyl)bicyclo[3.2.1]octane-2,4-dione (5.75 g, 20.6
mmol) was
dissolved in acetone (206 mL) to which potassium carbonate (4.34 g, 30.9 mmol)
was added.
lodomethane (6.42 mL, 103 mmol) was added dropwise to the reaction and stirred
at room
temperature under nitrogen for 22 hours. The reaction mixture was concentrated
in vacuo
and dichloromethane/water (300 mL) was added. The mixture was extracted twice
with
dichloromethane, dried over magnesium sulphate, filtered and reduced in vacuo
to afford 3-
(2-chloro-6-methoxy-phenyl)-2-methoxy-bicyclo[3.2.1]oct-2-en-4-one as a beige
solid after
trituration with diethyl ether.

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Step 5: Preparation of 342-chloro-6-methoxy-4-(4,4,5,5-tetramethy1-1,3,2-
dioxaborolan-2-
yl)phenyl]-2-methoxy-bicyclo[3.2.1]oct-2-en-4-one
0
CI
0 0
0
0
A mixture of 3-(2-chloro-6-methoxy-pheny1)-2-methoxy-bicyclo[3.2.1]oct-2-en-4-
one (25.00 g,
85.39 mmol), (1,5-cyclooctadiene)(methoxy)iridium(I) dimer (2.55 g, 3.84
mmol), 4,4'-di-tert-
buty1-2,2'-dipyridyl (2.11 g, 7.69 mmol) and bis(pinacolato)diboron (22.12 g,
85.39 mmol) was
evacuated and purged three times with nitrogen. Anhydrous tert-butyl methyl
ether (85.39
mL, 1 M) was added to the reaction mixture and refluxed at 80 C for 4 hours
under nitrogen.
The reaction mixture was concentrated onto silica gel for purification by
flash
chromatography (10-100% ethyl acetate in hexanes as eluant) to afford 3-[2-
chloro-6-
methoxy-4-(4,4,5,5-tetramethy1-1,3,2-dioxaborolan-2-yl)phenyl]-2-methoxy-
bicyclo[3.2.1]oct-
2-en-4-one as a pale yellow oil.
Step 6: Preparation of 3-(4-bromo-2-chloro-6-methoxy-
phenyl)bicyclo[3.2.1]octane-2,4-dione
CI B
0
0
r
342-chloro-6-methoxy-4-(4,4,5,5-tetramethy1-1,3,2-dioxaborolan-2-yl)phenyl]-2-
methoxy-
bicyclo[3.2.1]oct-2-en-4-one (5.00 g, 11.94 mmol) was dissolved in methanol
(120 mL) and
copper dibromide (5.33 g, 23.88 mmol) in water (120 mL) was added. The
reaction was
refluxed at 80 C under nitrogen for 1 hour. The reaction mixture was
concentrated under
vacuum to remove the methanol and diluted with dichloromethane (100 mL). The
phases
were separated and extracted twice with dichloromethane. The organics were
dried over

- 149 -
TM
magnesium sulphate, filtered through celite and reduced in vacuo. The crude
residue was
dissolved in acetone (120 mL) and 2M aqueous hydrochloric acid (120 mL) was
added. The
reaction mixture was heated at 60 C for 2 hours. The phases were extracted
three times
with dichloromethane, dried over magnesium sulphate, filtered and reduced in
vacuo. The
crude product was purified by flash column chromatography over silica gel (10-
100% ethyl
acetate in hexanes as eluant) to afford 3-(4-bromo-2-chloro-6-methoxy-
phenyl)bicyclo[3.2.1]octane-2,4-dione as an colourless solid.
Step 7: Preparation of 3-(2-chloro-6-methoxy-4-prop-1-ynyl-
phenyl)bicyclo[3.2.1]octane-2,4-
dione
CI
0
0
0
A mixture of 3-(4-bromo-2-chloro-6-methoxy-phenyl)bicyclo[3.2.1]octane-2,4-
dione (0.12 g,
0.34 mmol), dichlorobis(triphenylphosphine)palladium(II) (0.01 g, 0.017 mmol),
1,4-bis-
(diphenylphosphino)butane (0.014 g, 0.034 mmol) and but-2-ynoic acid (0.034 g,
0.40 mmol)
was evacuated and purged three times with nitrogen. Dimethylsulfoxide (4 mL)
was added to
the reaction mixture followed by tetrabutylammonium fluoride (1 M in
tetrahydrofuran, 1 mL,
1.00 mmol) and stirred at 110 C under nitrogen for 1 hour. The reaction
mixture was
quenched with 2M aqueous hydrochloric acid and extracted three times with
dichloromethane. The organics were dried over magnesium sulphate, filtered
over celite and
reduced in vacuo. The crude product was purified by flash column
chromatography over
silica gel (10-100% ethyl acetate in hexanes as eluant) to afford 3-(2-chloro-
6-methoxy-4-
prop-1-ynyl-phenyl)bicyclo[3.2.1]octane-2,4-dione as an colourless gum.
Example 8 : Preparation of 2-(2,6-dimethy1-4-prop-1-ynylpheny1)-5-(pyridin-2-
yl)cyclohexane-1,3-dione, hydrochloride salt
Date Recue/Date Received 2020-05-25

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/;-
0
0
N Ha
Step 1: Preparation of 2-(4-bromo-2,6-dimethylphenyI)-N-methoxy-N-
methylacetamide
/
Br
To a suspension of (4-bromo-2,6-dimethylphenyl)acetic acid (78.0g, 0.32m01)
(e.g. described
in DE 19603332) in anhydrous dichloromethane (1.3L) was added N-
hydroxybenzotriazole
(65.0g, 0.48m01) then 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide
hydrochloride (92.3g,
0.48m01) at 0 C under nitrogen. Diisopropylethylamine (165.8g, 1.28m01) was
then added
dropwise and the reaction mixture was stirred for approximately 15 minutes.
N,0-dimethyl
hydroxylamine hydrochloride (47.0g, 0.48m01) was next added, followed by
stirring at room
temperature for 4h. After dillution with dichloromethane (1L) the reaction
mixture was washed
with 2% aqueous hydrochloric acid solution, water then brine. The organic
layer was dried
over anhydrous sodium sulphate, solvents removed in vacuo, and the crude
product was
purified by flash column chromatography over silica gel (10-15% ethylacetate
in hexanes as
eluant). Further trituation with n-pentane afforded 2-(4-bromo-2,6-
dimethylphenyI)-N-
methoxy-N-methylacetamide as an off white solid.
Step 2: Preparation of 1-(4-bromo-2,6-dimethylphenyl)propan-2-one
Br
To a solution of 2-(4-bromo-2,6-dimethylpheny1)-N-methoxy-N-methylacetamide
(71.0g,
0.25m01) in anhydrous tetrahydrofuran was added methyl magnesium bromide
(355m1,

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- 151 -0.49mol, 1.4M solution in toluene) dropwise at 0 C. After stirring for
a further 10 minutes the
reaction was quenched by addition of saturated aqueous ammonium chloride at 0-
5 C. The
crude compound was extracted into ethyl acetate, washed with brine, dried over
anhydrous
sodium sulphate, and solvents were removed in vacuo. Purification by flash
column
chromatography over silica gel (3-5% ethylacetate in hexanes as eluant),
followed by
additional trituration with n-pentane afforded 1-(4-bromo-2,6-
dimethylphenyl)propan-2-one as
an off white solid.
Step 3: Preparation of 1-(4-bromo-2,6-dimethylpheny1)-4-(pyridin-2-yl)but-3-en-
2-one
Br
0
To a solution of 1-(4-bromo-2,6-dimethylphenyl)propan-2-one (26.7g, 110.7mm01)
in ethanol
(250m1) was added pyridine-2-carbaldehyde (11.9g, 110.72mmol) at room
temperature. 3.5M
aqueous sodium hydroxide (220m1) was then added dropwise at room temperature,
followed
by additional stirring for 5 minutes. The reaction mass was poured into water,
and the crude
product was extracted with ethyl acetate (3x 100m1). Organic fractions were
combined then
washed with brine, dried over anhydrous sodium sulphate, and solvents were
removed in
vacuo. Purification by flash column chromatography over silica gel (20%
ethylacetate in
hexanes as eluant), followed by additional trituration with n-pentane afforded
1-(4-bromo-2,6-
dimethylpheny1)-4-(pyridin-2-yl)but-3-en-2-one as a white solid.
Step 4: Preparation of 3-(4-bromo-2,6-dimethylpheny1)-2,4-dioxo-6-(pyridin-2-
yl)cyclohexanecarboxylic acid methyl ester
Br
OH
0
0 0
To a solution of sodium methoxide (7.2g, 33.2mm01) in anhydrous methanol
(150m1) was
added dimethyl malonate (17.6g, 133.24mm01), followed by stirring at room
temperature for

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minutes. 1-(4-Bromo-2,6-dimethylphenyI)-4-(pyridin-2-yl)but-3-en-2-one (20.0g,
60.6mmol) was then added and the reaction mixture was heated at reflux for 24
hours.
Organic solvents were removed in vacuo, and the residue was dissolved in water
then
washed with diethyl ether. The aqueous phase was acidified to pH 4-5 by slow
addition of
5 2% aqueous hydrochloric acid, and the resulting solid was dissolved in
dichloromethane,
washed with brine, dried over anhydrous sodium sulphate then concentrated in
vacuo. The
crude product was trituated with 1% diethylether in hexanes to afford 3-(4-
bromo-2,6-
dimethylpheny1)-2,4-dioxo-6-(pyridin-2-yl)cyclohexanecarboxylic acid methyl
ester as a white
solid.
Step 5: Preparation of 2-(4-bromo-2,6-dimethylphenyI)-5-(pyridin-2-
yl)cyclohexane-1,3-dione
Br
OH
0
A suspension of 3-(4-bromo-2,6-dimethylphenyI)-2,4-dioxo-6-pyridin-2-
ylcyclohexanecarboxylic acid methyl ester (23.0g, 53.5mmol) in 5M aqueous
sulfuric acid
(70m1) was heated at reflux for 4 hours. The reaction mixture was then cooled
to room
temperature and poured into ice water, and the pH was adjusted to 4-5 by
addition of 5%
aqueous hydrochloric acid. The crude product was trituated with diethylether
to afford 2-(4-
bromo-2,6-dimethylpheny1)-5-(pyridin-2-yl)cyclohexane-1,3-dione as an off
white solid.
Step 6: Preparation of 2-(4-bromo-2,6-dimethyl-pheny1)-3-methoxy-5-(2-
pyridyl)cyclohex-2-
en-1-one
Br
0
N
To a cooled (ice-bath) suspension of 2-(4-bromo-2,6-dimethyl-phenyI)-5-(2-
pyridyl)cyclohexane-1,3-dione (5.00 g, 13.4 mmol) in acetone (250 mL) was
added
potassium carbonate (2.78 g, 20.1 mmol) followed by iodomethane (9.53 g, 4.18
mL, 67.2
mmol). The mixture was stirred for 10 minutes and then cooling was removed and
solution
stirred at room temperature for 18 hours. Acetone was removed in vacuo and the
residue
was partitioned between water and ethyl acetate. The phases were separated and
the

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aqueous phase was extracted into ethyl acetate (x2). Combined organic phases
were
washed with brine, dried over magnesium sulphate, filtered and concentrated to
give an
orange gum which, after column chromatography on silica gel, afforded 2-(4-
bromo-2,6-
dimethyl-pheny1)-3-methoxy-5-(2-pyridyl)cyclohex-2-en-1-one (4.97 g, 12.9
mmol, 96%) as a
white solid.
Step 7: Preparation of 2-(2,6-dimethy1-4-prop-1-ynyl-pheny1)-3-methoxy-5-(2-
pyridy1)-
cyclohex-2-en-1-one
0
0
N
2-(4-bromo-2,6-dimethyl-pheny1)-3-methoxy-5-(2-pyridyl)cyclohex-2-en-1-one
(0.250 g, 0.647
mmol), cesium fluoride (0.197 g, 0.0478 mL, 1.29 mmol), cuprous iodide (0.0247
g, 0.129
mmol) and PdC12(dppf) (0.0710 g, 0.0971 mmol) were combined in a 2-5 mL
microwave vial
and which was sealed and purged with nitrogen. Dimethylformamide (1.9 g, 2 mL,
26 mmol)
was added followed by tributyl(prop-1-ynyl)stannane (0.852 g, 0.787 mL, 2.59
mmol). The
reaction was heated in the microwave at 120 C for 60 minutes. The reaction
mixture was
diluted with ethyl acetate and then poured into water. The biphasic mixture
was filtered
through diatomaceous earth and then the phases were separated. The aqueous
phase was
extracted into ethyl acetate (x2) then combined organic extracts were washed
with brine,
dried over magnesium sulphate, filtered and concentrated to a black residue
which, after
repeated column chromatography on silica gel, afforded 2-(2,6-dimethy1-4-prop-
1-ynyl-
pheny1)-3-methoxy-5-(2-pyridyl)cyclohex-2-en-1-one (0.216 g, 0.6253 mmol, 97%)
as a white
solid.
Step 8: Preparation of 2-(2,6-dimethy1-4-prop-1-ynylpheny1)-5-(pyridin-2-
y1)cyclohexane-1,3-
dione, hydrochloride salt

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- 154
0
0
N Ha
2-(2,6-dimethy1-4-prop-1-ynyl-pheny1)-3-methoxy-5-(2-pyridyl)cyclohex-2-en-1-
one (0.198 g,
0.5732 mmol) was dissolved in acetone (2.5 mL) in a 0.5-2 mL microwave vial.
2M aqueous
hydrochloric acid (0.2 mL, 0.4 mmol) was added and resultant solution was
heated in the
microwave at 70 to 90 C until LCMS (liquid chromatography-mass spectrometry)
analysis
indicated reaction had proceeded to completion. The reaction mixture was
concentrated in
vacuo to afford a beige solid which was azeotroped with toluene to afford 2-
(2,6-dimethy1-4-
prop-1-ynyl-pheny1)-5-(pyridin-2-yl)cyclohexane-1,3-dione hydrochloride
(0.1864 g, 0.5067
mmol, 88%) as a pale pink solid.
Example 9 : Preparation of 2-(2,6-dimethy1-4-prop-1-ynylpheny1)-3-
(methoxycarbonyloxy)-5-(pyridin-2-y1)cyclohex-2-en-1-one
OIII0 0
0
N
To a solution of 2-(2,6-dimethy1-4-prop-1-ynyl-pheny1)-5-(pyridin-2-
y1)cyclohexane-1,3-dione
hydrochloride (0.071 g, 0.193 mmol) in dichloromethane (2.0 mL) was added
triethylamine
(0.043 g, 0.059 mL, 0.425 mmol) followed by methyl carbonochloridate (0.022 g,
0.232
mmol) . Reaction mixture was stirred at room temperature for 18 hours. The
reaction
mixture was diluted with dichloromethane (2 mL) and water (2 mL) and then
passed through
a phase separation cartridge, washing with dichloromethane. The organic
filtrate was
concentrated in vacuo to afford [2-(2,6-dimethy1-4-prop-1-ynyl-pheny1)-3-oxo-5-
(pyridin-2-

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- 155 -
yl)cyclohexen-1-yl] methyl carbonate, which is also named 2-(2,6-dimethy1-4-
prop-1-
ynylpheny1)-3-(methoxycarbonyloxy)-5-(pyridin-2-Acyclohex-2-en-1-one, (0.072
g, 0.1849
mmol, 96% yield) as an orange solid.
Example 10: Preparation of 9-(2-Chloro-6-methoxy-4-prop-1-ynyl-phenyl)-3-oxa-
spiro[5.5]undecane-8,10-dione (Compound A-20)
CI
0
0
0
0
Step 1: Preparation of Diacetoxy-(2-chloro-6-methoxy-phenyl)plumbyl acetate
0¨\
=;.113
000
0
< \,õ
0
A solution of mercury (II) acetate (0.171 g) and lead (IV) acetate (5.70 g) in
chloroform (20
mL) under nitrogen atmosphere was warmed to 40 C. To this was added (2-chloro-
6-
methoxy-phenyl)boronic acid (2.00 g, CAS 385370-80-9) in a single portion and
heating at 40
C continued for 4 hours. The reaction was left to cool and stand overnight.
.. The reaction was diluted with chloroform (50 mL) and cooled in an ice bath.
Potassium
carbonate (13.3 g) was added gradually with stirring and the mixture stirred
for 5 minutes
under nitrogen. This mixture was filtered through Celite and washed through
with further
chloroform (80 mL). The filtrate was concentrated in vacuo to leave a dark
brown sticky
mass. Trituration with iso-hexane (40 mL) gave a solid which was filtered off
washed with a
little cold iso-hexane and air-dried to give diacetoxy-(2-chloro-6-methoxy-
phenyl)plumbyl
acetate (4.66 g) as a beige solid.
1H NMR (400 MHz, CDCI3 + a drop of d6-DMS0) 7.35-7.43 (m, 1H), 7.16 (t, 1H),
6.98-7.03
(dd, 1H), 3.88-3.93 (d, 3H), 2.08 (s, 9H).
Step 2: Preparation of 9-(2-Chloro-6-methoxy-phenyl)-3-oxa-spiro[5.5]undecane-
8,10-dione

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a
0
0
0
0
To a suspension of 3-oxaspiro[5.5]undecane-8,10-dione (0.40 g, CAS 1058731-65-
9) and 4-
(dimethylamino)pyridine (1.4 g) in chloroform (12 mL), under nitrogen
atmosphere was
added toluene (3 mL) followed by diacetoxy-(2-chloro-6-methoxy-phenyl)plumbyl
acetate (1.4
g). This mixture was heated, under nitrogen, at 69 C (internal temperature)
for 3.5 hours.
The reaction was left to cool and stand overnight.
The reaction mixture was diluted with chloroform (20 mL), cooled in an ice
bath and gradually
acidified with aqueous 2M hydrochloric acid (8 mL). After stirring vigorously
for 10 minutes a
pale orange suspension resulted. The mixture was filtered through water-washed
'Celite'
and washed through with chloroform. The organic layer was separated and
extracted with
aqueous sodium bicarbonate solution.
The aqueous layer was cooled in an ice-bath, acidified with aqueous 2M
hydrochloric acid,
extracted with dichloromethane (2x). The combined organic layers were dried
over
anhydrous magnesium sulfate. Concentration gave a thick oil, which was
purified by
chromatography on silica eluting with ethyl acetate in iso-hexane to give 9-(2-
chloro-6-
methoxy-phenyl)-3-oxaspiro[5.5]undecane-8,10-dione (0.429 g) as an off-white
solid
1H NMR (400 MHz, CDCI3) 7.28 (t, 1H), 7.08 (d, 1H), 6.84 (d, 1H), 5.85 (brs,
1H), 3.73 (s,
3H), 3.70 (t, 4H), 2.59 (brs, 4H), 1.75 (t, 2H), 1.70 (t, 2H)
The remaining steps to the desired compound 9-(2-chloro-6-methoxy-4-prop-1-
ynyl-phenyl)-
3-oxa-spiro[5.5]undecane-8,10-dione, Compound A-20, can be carried out
substantially as
described in Example 7.
Example 11: Preparation of 2-(2,6-Dimethy1-4-prop-1-ynyl-pheny1)-5-(2-
methylsulfanyl-
ethyl)cyclohexane-1,3-dione, Compound A-21
0
0

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- 157 -
Step 1: Preparation of (E)-6-Methylsulfanylhex-3-en-2-one
To a solution of 3-methylsulfanylpropanal (CAS 3268-49-3, 5.6 g) in
dichloromethane (120
mL) was added 1-(triphenylphosphoranylidene)-2-propanone (CAS 1439-36-7, 17 g)
in a
single portion. The reaction mixture was heated and stirred at reflux for 5
hours. The cooled
reaction mixture was concentrated to leave a pale yellow solid which was
triturated with a 1:1
mixture of ether:iso-hexane (100 mL). The resulting solid was collected by
filtration and
washed with further 1:1 ether:iso-hexane (50 mL). The filtrate was
concentrated to a yellow
oil and purified by chromatography on silica eluting with ethyl acetate in iso-
hexane to give
(E)-6-methylsulfanylhex-3-en-2-one (5.890 g) as a colourless liquid.
1H NMR (400 MHz, CDCI3) 6.81 (dt, 1H), 6.08-6.15 (m, 1H), 2.61-2.67 (m, 2H),
2.49-2.58 (m,
2H), 2.24-2.27 (m, 3H), 2.10-2.15 (m, 3H)
Step 2: Preparation of Ethyl 2-(2-methylsulfanylethyl)-4,6-dioxo-
cyclohexanecarboxylate
0 0
110
To ice cooled ethanol (50 mL) was added sodium metal (1.249 g) in small
portions under
nitrogen and the resulting solution was stirred for 15 minutes. Diethyl
propanedioate (7.901
g) in ethanol (25 mL) was added drop wise to this cooled solution over 20
minutes. The
reaction was allowed to warm to ambient temperature and stirred for a further
2 hours. The
mixture was cooled in an ice bath and a solution of (E)-6-methylsulfanylhex-3-
en-2-one
(5.890 g) in ethanol (25 mL) was added drop wise. The reaction was allowed to
warm to
ambient temperature, stirred for 4 hours and then left to stand overnight. The
reaction was
concentrated to a yellow slurry which was poured into a cooled solution of 2M
hydrochloric
acid and stirred for 5 minutes. This was extracted with dichloromethane (x2)
and the
combined organic layers dried over anhydrous magnesium sulfate and
concentrated to give
ethyl 2-(2-methylsulfanylethyl)-4,6-dioxo-cyclohexanecarboxylate (11.446 g) as
a yellow oil.
1H NMR (400 MHz, CDCI3) 5.48-5.56 (m, 1H), 4.13-4.33 (m, 2H), 3.38-3.48 (m,
1H), 3.11-

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3.21 (m, 1H), 2.44-2.75 (m, 3H), 2.17-2.26 (m, 1H), 2.09 (s, 3H), 1.63-1.86
(m, 2H), 1.30 (t,
3H)
Step 3: Preparation of 5-(2-Methylsulfanylethyl)cyclohexane-1,3-dione
0
S 0
A solution of ethyl 2-(2-methylsulfanylethyl)-4,6-dioxo-cyclohexanecarboxylate
(11.446 g) in
propan-2-ol (32 mL) was stirred with 2M sodium hydroxide solution (115.2 mL)
for 4 hours.
The reaction was concentrated to remove the propan-2-ol and the remaining
aqueous
solution was taken to pH 1 by the addition of conc. hydrochloric acid. This
solution was
heated to 70 C for 1.5 hours, then left to cool overnight. The resulting
solid was collected by
filtration and washed with water then iso-hexane and air dried to leave a pale
yellow powder.
The powder was washed further with water (x4) and air dried to give 5-(2-
methylsulfanylethyl)cyclohexane-1,3-dione (6.583 g) as a yellow solid
H NMR (400 MHz, CDCI3) 5.48 (s, 1H), 3.41 (d, 1H), 2.77 (dd, 3H), 2.45-2.61
(m, 2H), 2.25-
2.43 (m, 2H), 2.08-2.18 (m, 3H), 1.63-1.74 (m, 2H)
Step 4: Preparation of 2-(4-Bromo-2,6-dimethyl-phenyl)-5-(2-
methylsulfanylethyl)cyclohexane-1,3-dione
Br
0
A mixture of 5-(2-methylsulfanylethyl)cyclohexane-1,3-dione (0.425 g) and 4-
(dimethylamino)
pyridine (1.41 g) in chloroform (12 mL) was stirred under nitrogen for 10
minutes. Toluene (3
mL) was added followed by diacetoxy-(4-bromo-2,6-dimethyl-phenyl)plumbyl
acetate (1.56 g,
CAS 1160561-25-0). The resulting yellow suspension was heated under nitrogen
at 7500 for
3 hours. The reaction mixture was cooled in an ice bath and diluted with
dichloromethane (25
mL) and acidified with aqueous 2M hydrochloric acid (30 mL). After stirring
vigorously for 10
minutes the resulting white suspension was filtered through `Celite' then
washed through with

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dichloromethane. The organic layer was separated, dried over anhydrous
magnesium
sulfate and concentrated to leave an orange gum. The gum was purified by
chromatography
on silica eluting with ethyl acetate in iso-hexane to give 2-(4-bromo-2,6-
dimethyl-pheny1)-5-
(2-methylsulfanylethyl)cyclohexane-1,3-dione (0.496 g) as a white solid.
1H NMR (500 MHz, CDCI3) 7.28 (s, 2H), 5.46 (brs, 1H), 2.63-2.75 (m, 2H), 2.63-
2.75 (m,
2H), 2.56-2.61 (m, 2H), 2.36-2.47 (m, 2H), 2.17-2.29 (m, 1H), 2.10-2.14 (m,
3H), 2.07-2.09
(m, 3H), 1.75-1.83(m, 2 H)
Step 5: Preparation of 2-(2,6-Dimethy1-4-prop-1-ynyl-pheny1)-5-(2-
methylsulfanyl-
ethyl)cyclohexane-1,3-dione, Compound A-21
0
0
To a mixture of 2-(4-bromo-2,6-dimethyl-pheny1)-5-(2-
methylsulfanylethyl)cyclohexane-1,3-
dione (0.200 g), bis(triphenylphosphine)palladium(II) dichloride (CAS 13965-03-
2, 0.0192 g),
1,4-bis(diphenylphosphino)butane (CAS 7688-25-7, 0.0231 g) and but-2-ynoic
acid (0.0546
g) under nitrogen was added dimethyl sulfoxide (6.5 mL) and tetrabutylammonium
fluoride
(1M in tetrahydrofuran, 1.62 mL) and the mixture stirred at 110 C for 2
hours. The reaction
was cooled and partitioned between 2M hydrochloric acid and ethyl acetate. The
aqueous
layer was extracted with further ethyl acetate. The combined organic layers
were dried over
anhydrous magnesium sulfate, concentrated to an orange gum and purified by
chromatography on silica eluting with ethyl acetate in iso-hexane to give 2-
(2,6-dimethy1-4-
prop-1-ynyl-pheny1)-5-(2-methylsulfanylethyl)cyclohexane-1,3-dione (0.0548 g)
as a pale
yellow gum.
Example 12: Preparation of 2-(2-Chloro-6-methoxy-4-prop-1-ynyl-
phenyl)cyclohexane-
1,3-dione, Compound A-22

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0 CI
ci
o
Step 1: Preparation of 2-(4-Bromo-2-chloro-6-methoxy-phenyl)-3-methoxy-
cyclohex-2-en-1-
one
CI Br
0
o
To a solution of 2-(4-bromo-2-chloro-6-methoxy-phenyl)cyclohexane-1,3-dione
(0.86 g, which
can be prepared e.g. generally following procedures described in Examples 10
and 11) in
acetone (20 mL) was added potassium carbonate (0.85 g) followed by iodomethane
(0.81
mL) and water (2 pL). The reaction mixture was stirred at ambient temperature
overnight.
The mixture was partitioned between dichloromethane and water. The organic
layer was
reduced under vacuum to give 2-(4-bromo-2-chloro-6-methoxy-phenyl)-3-methoxy-
cyclohex-
2-en-1-one (0.7 g) as a yellow gum.
1H NMR (500 MHz, CDCI3) 7.17-7.22 (m, 1H), 6.93 (s, 1H), 3.73 (s, 3H), 3.70
(s, 3H), 2.70 (t,
2H), 2.45-2.54 (m, 2H), 2.09-2.18 (m, 2H).
Step 2: Preparation of 2-(2-Chloro-6-methoxy-4-prop-1-ynyl-phenyl)-3-methoxy-
cyclohex-2-
en-1-one
0
0
To a mixture of 2-(4-bromo-2,6-dimethyl-phenyl)-5-(2-
methylsulfanylethyl)cyclohexane-1,3-
dione (0.35 g), bis(triphenylphosphine)palladium(II) dichloride (CAS 13965-03-
2, 0.036 g),
1,4-bis(diphenylphosphino)butane (CAS 7688-25-7, 0.043 g) and but-2-ynoic acid
(0.102 g)
under nitrogen was added dimethyl sulfoxide (8 mL) and tetrabutylammonium
fluoride (1M in
tetrahydrofuran, 3.04 mL) and the mixture stirred at 110 C for 2 hours. The
reaction was

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cooled and partitioned between 2M hydrochloric acid and extracted with ethyl
acetate. The
aqueous layer was extracted with further ethyl acetate. The combined organic
layers were
dried over anhydrous magnesium sulfate, concentrated to an orange gum and
purified by
chromatography on silica eluting with ethyl acetate in iso-hexane to give 2-(2-
chloro-6-
methoxy-4-prop-1-ynyl-phenyl)-3-methoxy-cyclohex-2-en-1-one (0.18 g) as a
yellow gum.
1H NMR (500 MHz, CDCI3) 7.06 (d, 1H), 6.81 (d, 1H), 3.71 (s, 3H), 3.67 (s,
3H), 2.69 (td, 2H),
2.46-2.51 (m, 2H), 2.08-2.17 (m, 2H), 2.02-2.05 (m, 3H).
Step 3: Preparation of 2-(2-Chloro-6-methoxy-4-prop-1-ynyl-phenyl)cyclohexane-
1,3-dione
CI
0
To a solution of 2-(2-chloro-6-methoxy-4-prop-1-ynyl-phenyl)-3-methoxy-
cyclohex-2-en-1-
one (0.18 g) in acetone (2 mL) was added 2M hydrochloric acid (2 mL) and the
mixture
heated to 60 C for 1 hour. The reaction mixture was reduced under vacuum at
500mbar.
The remaining aqueous solution was partitioned with dichloromethane. The
organic layer
was concentrated to give 2-(2-chloro-6-methoxy-4-prop-1-ynyl-
phenyl)cyclohexane-1,3-dione
(0.18 g) as a cream solid.
Example 13: Preparation of 2-(2-Chloro-6-methoxy-4-prop-1-ynyl-phenyl)-5-(2-
methylsulfanylethyl)cyclohexane-1,3-dione, Compound A-23
CI
0
o 0`-
Step 1: Preparation of 5-Bromo-1-chloro-2-iodo-3-methoxy-benzene
CI O
Br

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Dry methanol (160 mL) was cooled to 10 C and potassium hydroxide (14.99) was
added
portion wise over 25 minutes. Once dissolved, this solution was added over 15
minutes to a
refluxing solution of 5-bromo-1-chloro-3-fluoro-2-iodo-benzene (CAS 83027-73-
0, 40.0 g) in
dry methanol (320 mL). After 46 hours refluxing the reaction mixture was
concentrated and
partitioned between water (500 mL) and ethyl acetate (500 mL). The aqueous
phase was
extracted with further ethyl acetate (2 x 200 mL). The combined organic layers
were washed
with brine (400 mL), dried over magnesium sulfate, concentrated and purified
by
chromatography on silica eluting with ethyl acetate in iso-hexane to give 5-
bromo-1-chloro-2-
iodo-3-methoxy-benzene (37.767 g) as a pale pink solid
1H NMR (500 MHz, CDCI3) 7.28 (d, 1H), 6.82 (d, 1H), 3.90 (s, 3H).
Step 2: Preparation of (4-Bromo-2-chloro-6-methoxy-phenyl)boronic acid
0 Br
A solution of 5-bromo-1-chloro-2-iodo-3-methoxy-benzene (15.0 g) in dry
tetrahydrofuran
(173 mL) was cooled to -78 C under nitrogen. A solution of isopropyl magnesium
chloride
(2M in tetrahydrofuran, 43.2 mL) was added dropwise over 30 minutes,
maintaining an
internal temperature below -65 C. The reaction mixture was stirred at -78 C
for 25 minutes
and then allowed to warm to ambient temperature with stirring. After
approximately 2 hours
the reaction solution was cooled to -70 C and trimethyl borate (14.4 g) was
added dropwise
over 15 minutes. On completion of addition, the solution was stirred at -78 C
for 20 minutes
and then the cooling was removed and mixture stirred for 18 hours. The
reaction mixture
was diluted with water (50 mL) and acidified with 2M hydrochloric acid (150
mL) and stirred
for 2 hours. Ethyl acetate was added and the layers were separated. The
aqueous was
extracted with further ethyl acetate (x2) then the combined organic phases
were washed with
brine, dried over magnesium sulfate and concentrated to afford an orange-brown
residue.
This residue was dissolved in ethyl acetate (200 mL) and washed sequentially
with 4:1
water:saturated aqueous sodium thiosulfate solution (2 x 100 mL), water (100
mL) and brine
(100 mL), dried over magnesium sulfate and concentrated to a pale yellow
solid. This
sample was triturated with iso-hexane (100 mL) and the solid filtered off,
washed with further
iso-hexane and air-dried to give (4-bromo-2-chloro-6-methoxy-phenyl)boronic
acid (10.160 g)

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as a white solid.
1H NMR (500 MHz, 0D0I3 + 3 drops CD30D) 7.11 (m, 1H), 6.87 (m, 1H), 3.77 (s,
3H)
Step 3: Preparation of (4-Bromo-2-chloro-6-methoxy-phenyl)-diisopropoxy-borane
CI Br
0 0
A solution of (4-bromo-2-chloro-6-methoxy-phenyl)boronic acid (2.00 g) in
propan-2-ol (13
mL) and toluene (13 mL) was refluxed using a Dean-Stark apparatus for 24
hours. The
reaction mixture was concentrated to give (4-bromo-2-chloro-6-methoxy-phenyl)-
diisopropoxy-borane (2.612 g) as a pale orange oil.
1H NMR (500 MHz, CDCI3) 7.11 (s, 1H), 6.87 (s, 1H), 4.25 (sept, 2H), 3.78 (s,
3H), 1.19 (d,
6H).
Step 4: Preparation of Diacetoxy-(4-bromo-2-chloro-6-methoxy-phenyl)plumbyl
acetate
CI Br
0 0
0
< `)\.
0
A mixture of mercury (II) trifluoroacetate (0.310 g) and lead (IV) acetate
(1.898 g) in
chloroform (20 mL) under nitrogen was warmed to 40 C with stirring. Heating
was removed
and a solution of (4-bromo-2-chloro-6-methoxy-phenyl)-diisopropoxy-borane
(1.248 g) in
chloroform (3 mL) was added over 5 minutes. This mixture was heated 55 C for
3 hours and
left to cool overnight. The reaction mixture was cooled in an ice bath to 5 C
and chloroform
(20 mL) added. To this suspension was added potassium carbonate (2.221 g) and
the
mixture stirred for 10 minutes. The suspension was filtered through chloroform
washed
rCelite' and washed through with fresh chloroform (50 mL). The pale yellow
filtrate was
concentrated to leave a pale brown solid. This solid was triturated with iso-
hexane and a
little chloroform, filtered, washed with iso-hexane and air-dried to give
diacetoxy-(4-bromo-2-
chloro-6-methoxy-phenyl)plumbyl acetate (1.466 g) as a pale pink-beige solid.
1H NMR (500 MHz, CDCI3) 7.32 (s, 1H), 7.10 (s, 1H), 3.92 (s, 3H), 2.10 (s,
9H).

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Step 5: Preparation of 2-(4-Bromo-2-chloro-6-methoxy-phenyl)-5-(2-
methylsulfanylethyl)cyclohexane-1,3-dione
CI Br
0
0
0
A mixture of 5-(2-methylsulfanylethyl)cyclohexane-1,3-dione (0.375 g) and 4-
(dimethylamino)
pyridine (1.24 g) in chloroform (15 mL) was stirred under nitrogen for 10
minutes. Toluene (4
mL) was added followed by diacetoxy-(4-bromo-2-chloro-6-methoxy-phenyl)plumbyl
acetate
(1.46 g). The resulting yellow suspension was heated under nitrogen at 75 C
for 5 hours.
The reaction mixture was cooled in an ice bath and acidified with aqueous 2M
hydrochloric
acid. After stirring vigorously for 10 minutes the resulting white suspension
was filtered
through rCelite' then washed through with dichloromethane. The organic layer
was
separated, dried over anhydrous magnesium sulfate and concentrated to leave an
orange
solid. The solid was purified by chromatography on silica eluting with ethyl
acetate in iso-
hexane to give 2-(4-bromo-2-chloro-6-methoxy-phenyl)-5-(2-
methylsulfanylethyl)cyclohexane-1,3-dione (0.456 g) as a white foam.
1H NMR (500 MHz, CD30D) 7.18-7.26 (m, 1H), 7.09 (t, 1H), 3.76 (d, 3H), 2.58-
2.68 (m, 4H),
2.32-2.45 (m, 3H), 2.12-2.18 (m, 3H), 1.76-1.86 (m, 2H)
The remaining step to the desired compound, 2-(2-chloro-6-methoxy-4-prop-1-
ynyl-phenyl)-
5-(2-methylsulfanylethyl)cyclohexane-1,3-dione, Compound A-23 can e.g. be
carried out
substantially as described in Example 11.
Example 14: Preparation of 2-(2,6-Dimethyl-4-prop-1-ynyl-phenyl)-5-(2-
methylsulfanylpropyl)cyclohexane-1,3-dione, Compound A-24

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0
0
Step 1: Preparation of (E)-6-Methylsulfanylhept-3-en-2-one
0
To a solution of 3-methylsulfanylbutanal (CAS 16630-52-7, 6.4 g) in
dichloromethane (120
mL) was added 1-(triphenylphosphoranylidene)-2-propanone (CAS 1439-36-7, 17 g)
in a
single portion. The reaction mixture was heated and stirred at reflux for 7
hours and left to
cool overnight. The cooled reaction mixture was concentrated to leave a pale
yellow solid
which was triturated with a 1:1 mixture of ether:iso-hexane (100 mL). The
resulting solid was
collected by filtration and washed with further 1:1 ether:iso-hexane (50 mL).
The filtrate was
concentrated to a yellow oil and purified by chromatography on silica eluting
with ethyl
acetate in iso-hexane to give (E)-6-methylsulfanylhept-3-en-2-one (5.409 g) as
a yellow
liquid.
1H NMR (400 MHz, CDCI3) 6.82 (dt, 1H), 6.12 (d, 1H), 2.84 (sxt, 1H), 2.37-2.56
(m, 2H), 2.27
(s, 3H), 2.08-2.14 (m, 3H), 1.27-1.34 (m, 3H)
Step 2: Preparation of Ethyl 2-(2-methylsulfanylpropyI)-4,6-dioxo-
cyclohexanecarboxylate
0 =
0
To ice cooled ethanol (50 mL) was added sodium metal (1.045 g) in small
portions under
.. nitrogen, and the resulting solution was stirred for 15 minutes. Diethyl
propanedioate (6.613
g) in ethanol (25 mL) was added drop wise to this cooled solution over 20
minutes. The
reaction was allowed to warm to ambient temperature and stirred for a further
1 hour. The
mixture was cooled in an ice bath and a solution of (E)-6-methylsulfanylhept-3-
en-2-one
(5.409 g) in ethanol (25 mL) was added drop wise. The reaction was allowed to
warm to

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ambient temperature, stirred for 4 hours and then left to stand overnight. The
reaction was
concentrated to a yellow slurry which was poured into a cooled solution of 2M
hydrochloric
acid and stirred for 5 minutes. This was extracted with dichloromethane (x2)
and the
combined organic layers were dried over anhydrous magnesium sulfate,
concentrated and
purified by chromatography on silica eluting with ethyl acetate in iso-hexane
to give ethyl 2-
(2-methylsulfanylpropy1)-4,6-dioxo-cyclohexanecarboxylate (3.227 g) as a
yellow oil.
1H NMR (400 MHz, CDCI3) 5.38-5.43 (m, 1H), 4.13-4.31 (m, 2H), 3.86-3.96 (m,
2H), 3.05-
3.18 (m, 1H), 2.53-2.88 (m, 2H), 2.12-2.37 (m, 1H), 1.99-2.09 (m, 3H), 1.44-
1.75 (m, 2H),
1.22-1.41 (m, 6H).
Step 3: Preparation of 5-(2-Methylsulfanylpropyl)cyclohexane-1,3-dione
so
A mixture of 3-ethoxy-5-(2-methylsulfanylpropyl)cyclohex-2-en-1-one (5.846 g)
was heated
and stirred in 5M hydrochloric acid (30 mL) for 6 hours and left to stand
overnight. The
reaction mixture was extracted with ethyl acetate (x2). The combined organic
layers were
dried over anhydrous magnesium sulfate, concentrated and purified by
chromatography on
silica eluting with ethyl acetate in iso-hexane to give 5-(2-
methylsulfanylpropyl)cyclohexane-
1,3-dione (1.734 g) as a white solid
1H NMR (400 MHz, CDCI3) 7.55 (brs, 1H), 3.41 (d, 1H), 2.65-2.82 (m, 2H), 2.33-
2.55 (m,
3H), 2.01-2.16 (m, 4H), 1.42-1.67 (m, 2H), 1.24-1.33 (m, 3H)
The remaining steps to 2-(2,6-dimethy1-4-prop-1-ynyl-pheny1)-5-(2-
methylsulfanylpropyl)cyclohexane-1,3-dione, Compound A-24, can e.g. be carried
out using
substantially the methods described in Example 11.
Example 15: Preparation of 342-Chloro-4-(2-chloroethyny1)-6-methoxy-
phenyl]bicyclo[3.2.1]octane-2,4-dione, Compound A-25
0 CI
o 0

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Step 1: Preparation of 3-(2-Chloro-4-ethyny1-6-methoxy-phenyl)-2-methoxy-
bicyclo[3.2.1]oct-
2-en-4-one
C
0
o 0
To a solution of 3-(2-chloro-4-ethyny1-6-methoxy-phenyl)bicyclo[3.2.1]octane-
2,4-dione
(0.200 g, Compound B-3) in acetone (6.6 mL) was added potassium carbonate
(0.139 g).
lodomethane (0.206 mL) was added and the reaction mixture stirred at room
temperature for
16 hours. The organic layer was concentrated and purified by chromatography on
silica
eluting with ethyl acetate in iso-hexane to give 3-(2-chloro-4-ethyny1-6-
methoxy-phenyl)-2-
methoxy-bicyclo[3.2.1]oct-2-en-4-one (0.200 g).
1H NMR (500 MHz, CDCI3) 7.16 (m, 1H), 6.88 (m, 1H), 3.73 (d, 3H), 3.64 (d,
3H), 3.20 (m,
1H), 3.07 (s, 1H), 3.02 (d, 1H), 2.25 (d, 1H), 2.07-2.17 (m, 2H), 1.78-2.02
(m, 2H), 1.63-1.71
(m, 1H).
Step 2: Preparation of 342-Chloro-4-(2-chloroethyny1)-6-methoxy-
phenyl]bicyclo[3.2.1]octane-2,4-dione, Compound A-25
CI
CI
0
0 ()
To a solution of 3-(2-chloro-4-ethyny1-6-methoxy-phenyl)-2-methoxy-
bicyclo[3.2.1]oct-2-en-4-
one (0.095 g) in carbon tetrachloride (0.9 mL) was added potassium carbonate
(0.046 g) and
tetrabutylammonium fluoride trihydrate (0.019 g). The mixture was stirred at
room
temperature for 3 hours. Further tetrabutylammonium fluoride trihydrate (0.020
g) was
added and stirring continued for 1 hour. After this time further
tetrabutylammonium fluoride
trihydrate (0.020 g), potassium carbonate (0.046 g) and carbon tetrachloride
(1 mL) were
added and the mixture stirred for 1 hour and then left to stand overnight. The
reaction
mixture was concentrated and the residue was dissolved in acetone (3 mL). To
this was
added 2M hydrochloric acid (3 mL) and the mixture heated at 60 C for 3 hours.
The reaction

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mixture was extracted with ethyl acetate (x2) and the combined organic layers
were washed
with brine, dried over anhydrous magnesium sulfate and concentrated. The
residue was
purified by chromatography on silica eluting with ethyl acetate in iso-hexane
to give 3-[2-
chloro-4-(2-chloroethyny1)-6-methoxy-phenyl]bicyclo[3.2.1]octane-2,4-dione,
Compound A-25
(0.0937 g).
Example 16: Preparation of [342-Chloro-4-prop-1-yny1-6-(2,2,2-
trifluoroethoxy)pheny1]-
4-oxo-2-bicyclo[3.2.1]oct-2-enyl] ethylsulfanylformate, Compound P-6
0
CI
0j<F
0
To a suspension of 342-chloro-4-prop-1-yny1-6-(2,2,2-
trifluoroethoxy)phenyllbicyclo[3.2.1]octane-2,4-dione (Compound A-19, 0.04 g)
in
dichloromethane (2 mL) was added pyridine (0.0168 mL) and 4-
(dimethylamino)pyridine
(0.001 g) and the mixture stirred for 5min. S-ethyl chlorothioformate (0.0169
mL) was added
and the reaction mixture was stirred for 2 hours. The reaction mixture was
evaporated to a
gum and purified on silica eluting with 10% ether in iso-hexane to give [342-
chloro-4-prop-1-
yny1-6-(2,2,2-trifluoroethoxy)pheny11-4-oxo-2-bicyclo[3.2.1]oct-2-enyl]
ethylsulfanylformate
(0.041 g) as a white solid.
Example 17: Preparation of 9-(2-Chloro-4-ethyny1-6-methoxy-phenyl)-3-
oxaspiro[5.5]undecane-8,10-dione, Compound B-1
CI
0
0
0
0
Step 1: Preparation of 942-Chloro-6-methoxy-4-(2-trimethylsilylethynyl)pheny1]-
3-
oxaspiro[5.5]undecane-8,10-dione

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I
si
I
0
0
0
0
To a suspension of 9-(4-bromo-2-chloro-6-methoxy-phenyl)-3-
oxaspiro[5.5]undecane-8,10-
dione (0.050 g, e.g. see Example 10) in toluene (2.1 mL) was added [1,1'-
bis(diphenylphosphino)ferrocene]dichloro-palladium(II) dichloromethane complex
(0.0051 g)
and trimethyl(2-tributylstannylethynyl)silane (0.072 g) and the mixture heated
at reflux for 3.5
hours. The reaction was cooled, diluted with ethyl acetate and filtered
through water-washed
'Celite'. This was washed through with further ethyl acetate and water. The
layers were
partitioned and the aqueous extracted with further ethyl acetate. The combined
organic
layers were washed with water, brine and dried over anhydrous magnesium
sulfate,
concentrated to an orange gum and purified by chromatography on silica eluting
with ethyl
acetate in iso-hexane to give 942-chloro-6-methoxy-4-(2-
trimethylsilylethynyl)pheny1]-3-
oxaspiro[5.5]undecane-8,10-dione (0.041 g) as a brown sticky gum.
1H NMR (500 MHz, CDCI3) 7.20 (s, 1H), 6.90 (s, 1H), 5.90 (s, 1H), 3.74 (s,
3H), 3.70 (t, 4H),
2.59 (m, 4H), 1.75 (t, 2H), 1.68 (t, 2H), 0.25 (s, 9H).
Step 2: Preparation of 9-(2-Chloro-4-ethyny1-6-methoxy-phenyl)-3-
oxaspiro[5.5]undecane-
8,10-dione, Compound B-1
GI
0
o 0
0
To a solution of 942-chloro-6-methoxy-4-(2-trimethylsilylethynyl)pheny1]-3-
oxaspiro[5.5]undecane-8,10-dione (0.11 g) in methanol (5.25 mL) was added
potassium
carbonate (0.053 g) and the suspension was stirred for 2 hours and left to
stand overnight.
Water (25 mL) was added and the mixture washed with ethyl acetate. The aqueous
layer
was acidified with a few drops of conc. hydrochloric acid and stirred for 15
minutes. The
aqueous mixture was extracted with ethyl acetate. The organic layer was
separated, washed
with water, dried over anhydrous magnesium sulfate and concentrated to an
orange gum.
Trituration with cold ether gave a solid which was filtered off and air-dried
to give 9-(2-chloro-
4-ethyny1-6-methoxy-phenyl)-3-oxaspiro[5.5]undecane-8,10-dione (0.072 g) as a
beige solid.

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Example 18: Preparation of 2-(2-Chloro-4-ethyny1-6-methoxy-phenyl)-3-hydroxy-
cyclohex-2-en-1-one, Compound B-2
<==
o
Step 1: Preparation of 242-Chloro-6-methoxy-4-(2-trimethylsilylethynyl)pheny1]-
3-methoxy-
cyclohex-2-en-1-one
CI
o
To a suspension of 2-(4-bromo-2-chloro-6-methoxy-pheny1)-3-methoxy-cyclohex-2-
en-1-one
(0.35 g, e.g. see Example 12, Step 1) in toluene (17.22 mL) was added [1,1'-
bis(diphenylphosphino)ferrocene]dichloro-palladium(II) dichloromethane complex
(0.042 g)
and trimethyl(2-tributylstannylethynyl)silane (0.5883 g) under nitrogen. The
mixture was
heated at reflux for 3 hours. The reaction mixture was partitioned between
dichloromethane
and water. The organic layer was concentrated and purified by chromatography
on silica
eluting with ethyl acetate in iso-hexane to give 2-[2-chloro-6-methoxy-4-(2-
trimethylsilylethynyl)phenyI]-3-methoxy-cyclohex-2-en-1-one (0.200 g) as a
yellow gum.
1H NMR (500 MHz, CDCI3) 7.13-7.17 (m, 1H), 6.86 (s, 1H), 3.73 (s, 3H), 3.66
(s, 3H), 2.69 (t,
2H), 2.45-2.52 (m, 2H), 2.11-2.17 (m, 2H)
Step 2: Preparation of 2-(2-Chloro-4-ethyny1-6-methoxy-pheny1)-3-hydroxy-
cyclohex-2-en-1-
one
0
0
0
To a solution of 242-chloro-6-methoxy-4-(2-trimethylsilylethynyl)pheny1]-3-
methoxy-cyclohex-

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- 171 -2-en-1-one (0.200 g) in methanol (11.02 mL) was added potassium
carbonate (0.116 g).
After stirring for 2 hours the reaction mixture was partitioned between
dichloromethane and
water. The aqueous layer was acidified with conc. hydrochloric acid and
extracted with
dichloromethane. The organic layer was concentrated to give 2-(2-chloro-4-
ethyny1-6-
methoxy-phenyl)-3-hydroxy-cyclohex-2-en-1-one, Compound B-2 (0.064 g) as an
orange
foamy solid.
Example 19: Preparation of 3-(2-Chloro-4-ethyny1-6-methoxy-
phenyl)bicyclo[3.2.1]octane-2,4-dione, Compound B-3
Step 1: Preparation of 342-Chloro-6-methoxy-4-(2-
trimethylsilylethynyl)phenyl]bicyclo[3.2.1]octane-2,4-dione
I
Si
0
0
A mixture of 3-(4-bromo-2-chloro-6-methoxy-phenyl)bicyclo[3.2.1]octane-2,4-
dione (Example
7 Step 6, 0.500 g,), trimethyl(2-tributylstannylethynyl)silane (0.812 g) and
[1,1-
bis(diphenylphosphino)ferrocene]dichloro-palladium(11) dichloromethane complex
(0.0569 g)
was dissolved in toluene (17 mL) and the mixture vigorously refluxed for 3
hours under air.
The reaction mixture was filtered through `Celite', washing through with ethyl
acetate. Water
was added to the filtrate and the mixture partitioned. The aqueous layer was
extracted with
further ethyl acetate (x3). The combined organic layers were washed with
brine, dried over
anhydrous magnesium sulfate, concentrated and purified by chromatography on
silica eluting
with ethyl acetate in iso-hexane to give 342-chloro-6-methoxy-4-(2-
trimethylsilylethynyl)phenyl]bicyclo[3.2.1]octane-2,4-dione (0.305 g).
1H NMR (CDC13) 7.19 (m, 1H), 6.89 (m, 1H), 5.48-5.67 (m, 1H), 3.75 (d, 3H),
2.96-3.07 (m,

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2H), 2.26 (d, 1H), 2.07-2.18 (m, 2H), 1.74-2.03 (m, 2H), 1.65 (dm, 1H), 0.25
(s, 9H).
Step 2: Preparation of 3-(2-Chloro-4-ethyny1-6-methoxy-
phenyObicyclo[3.2.1]octane-2,4-
dione
0
0
To a solution of 342-chloro-6-methoxy-4-(2-
trimethylsilylethynyl)phenyl]bicyclo[3.2.1]octane-
2,4-dione (0.270 g) in methanol (7.2 mL) was added potassium carbonate (0.303
g) and the
mixture stirred for 2 hours. The reaction mixture was concentrated and
partitioned between
water and dichloromethane. The aqueous layer was washed with further
dichloromethane
and then acidified using 2M hydrochloric acid and extracted with
dichloromethane (x2). The
combined organic layers were dried over anhydrous magnesium sulfate and
concentrated to
give 3-(2-chloro-4-ethyny1-6-methoxy-phenyl)bicyclo[3.2.1]octane-2,4-dione,
Compound B-3
(0.2165 g) as a pale yellow solid.

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Additional compounds in Table Ti below illustrate the present invention, and
are particular
embodiments of the compounds of formula (I) according to the present
invention. For the
most part, these compounds can generally be prepared by methods similar to
those shown in
the Examples and/or shown in the process section hereinabove using appropriate
starting
materials.
Table T1
Compound Structure 1H NMR data (in CDCI3 solvent
Number unless stated) or other physical data
6 (delta) 7.34 (d, 1H), 7.29 (dd, 1H),
0 7.01 (d, 1H), 5.37-5.81 (br. s),
2.1 (s,
A-1 3H), 2.06 (s, 3H), 1.4-1.68 (m,
12H).
0
0
6 (delta) (d4-Me0D) 7.17 (m, 1H),
7.10 (m, 1H), 6.86 (d, 0.5H, isomer
0
A-2 A), 6.81 (d, 0.5H, isomer B), 2.97 (q,
2H), 1.71-2.26 (m, 11H), 1.67 (m,
1H, isomer A or B).
0
6 (delta) 7.16-7.13 (m, 2H), 5.31-
5.27 (m, 1H), 3.11-3.03 (m, 2H),
0 2.37-2.15 (m, 6H), 2.08 (s, 2H),
2.04
A-3 (s, 3H), 1.96 (s, 1H), 1.86-1.67 (m,
2H), 1.48-1.32 (m, 2H), 0.92-0.85
0 (m, 3H).
6 (delta) 7.35-7.31 (m, 1H), 7.23-
7.20 (m, 1H), 5.40-5.33 (m, 1H),
0 3.12-3.01 (m, 2H), 2.51-2.26 (m,
A-4 3H), 2.24-2.12 (m, 3H), 2.01-1.86
(m, 2H), 1.74-1.67 (m, 1H), 1.28-
CI
0 1.24 (m, 2H), 1.13-1.04 (m, 3H).

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Compound Structure 1H NMR data (in CDCI3 solvent
Number unless stated) or other physical data
6 (delta) (d4-Me0D) 7.02-6.99 (m,
2H), 2.99-2.95 (m, 2H), 2.23-2.17
0
(m, 3H), 2.03 (s, 3H), 1.98 (s, 3H),
A-5
1.92 (s, 3H), 1.83-1.79 (m, 2H),
1.73-1.66 (m, 1H).
0
CI
6 (delta) (d4-Me0D) 7.10 (d, 2H),
0 3.01-2.95 (m, 2H), 2.25-2.18 (m,
A-6 3H), 2.06 (s, 3H), 1.94 (s, 3H), 1.86-
1.79 (m, 2H), 1.73-1.66 (m, 1H).
0
CI
6 (delta) 7.41 (d, 1H), 7.34 (dd, 1H),
0 7.05 (d, 1H), 2.1 (s, 3H), 1.37-1.83
A-7
(br s, 12H).
0
0 6 (delta) 7.20 (s, 2H), 3.96 (dd, 2H),
0 3.39 (dd, 2H), 2.62 (dd, 2H), 2.37
A-8 (dd, 2H), 2.20 (m, 1H), 2.07 (s, 3H),
0
2.04 (s, 3H), 1.62 (m, 3H), 1.42 (m,
Cl 2H), 1.32 (m, 2H).
6 (delta) 7.13 (s, 2H), 6.15-6.25
0 (br.$), 3.94 (dd, 2H), 3.39 (dd, 2H),
A-9 0 2.60 (dd, 2H), 2.34 (dd, 2H), 2.22
(m, 1H), 2.05 (s, 3H), 2.03 (s, 3H),
0 2.02 (s, 3H), 1.62 (m, 3H), 1.40 (m,
2H), 1.31 (m, 2H).

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Compound Structure 1H NMR data (in CDCI3 solvent
Number unless stated) or other physical data
6 (delta) 6.94-6.92 (m, 1 H), 6.79-
6.78 (m, 1 H), 3.71-3.69 (m, 3 H),
0
3.02-3.01 (m, 2 H), 2.31-2.28 (m, 1
A-10
H), 2.20-2.13 (m, 2 H), 2.08-1.97 (m,
6 H), 1.93-1.81 (m, 2 H), 1.65 (dtd, J
0 C) = 11.3, 4.4, 1.4 Hz, 1 H).
6 (delta) 7.48-7.46 (m, 1 H), 7.31-
7 .26 (m, 2 H), 7.08-7.01 (m, 1 H),
A-11 0
5.95 (br, 1 H), 3.05-3.02 (m, 2 H),
2.28-2.13 (m, 4 H), 2.05 (s, 3 H),
1.94 (br, 1 H), 1.69-1.62 (m, 1 H).
0
6 (delta) 7.12-7.09 (m, 1 H), 6.84-
6.83 (m, 1 H), 5.66-5.53 (m, 1 H),
CI
3.74-3.72 (m, 3 H), 3.04-3.01 (m, 2
A-12 H), 2.28-2.25 (m, 1 H), 2.13-2.09 (m,
2 H), 2.05 (s, 3 H), 2.04-1.94 (m, 1
0 () H), 1.89-1.76 (m, 1 H), 1.67-1.63 (m,
1 H).
6 (delta) (d4 Me0D): 8.80 (d, 1H),
0 8.59 (td, 1H), 8.14 (d, 1H), 7.97 (t,
1H), 7.07 (d, 2H), 4.05 - 3.98 (m,
A-13 1H), 3.11 (dd, 2H), 2.95 (dd, 2H),
0 2.09 (s, 3H), 2.00 (app. d, 6H).
HCI
0 6 (delta) 8.60 (d, 1H), 7.69 (td, 1H),
r" 7.28 - 7.27 (m, 1H), 7.21 (dd, 1H),
0 0
7.08 (d, 2H), 3.78 - 3.74 (m, 1H),
A-14 3.66 (s, 3H), 3.38 (dd, 1H), 3.10
0 3.01 (m, 2H), 2.93 - 2.89 (m, 1H),
2.10 (s, 3H), 2.03 (s, 3H), 1.98 (s,
N
3H).

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Compound Structure 1H NMR data (in CDCI3 solvent
Number unless stated) or other physical data
0 6 (delta) 8.60 (d, 1H), 7.69 (td, 1H),
7.28 - 7.27 (m, 1H), 7.21 (dd, 1H),
-)L0
7.08 (d, 2H), 3.78 - 3.73 (m, 1H),
A-15 3.33 (dd, 1H), 3.06 (dd, 1H), 2.99
0 2.88 (m, 2H), 2.09 (s, 3H), 2.04 (s,
3H), 1.98 (s, 3H), 1.86 (s, 3H).
N
X-4 6 (delta) (d4 Me0D): 8.70 (dd, 1H),
(Reference o 8.28 (td, 1H), 7.87 (d, 1H), 7.70
compound; (ddd, 1H), 7.16 (d, 2H), 3.94 - 3.87
Comparator (m, 1H), 3.38 (s, 1H), 3.13 - 3.06 (m,
compound;o
0 2H), 2.93 - 2.88 (m, 2H), 2.12 (s,
to be 3H), 2.01 (s, 3H).
OH
compared
with A-13)
6 (delta) (d4 Me0D): 6.99 (dd, 1 H),
CI 6.81 - 6.87 (m, 1 H), 3.94 (dq, 2 H),
0
2.98 (br. s., 2 H), 2.13 -2.27 (m, 3
A-16
H), 2.03 (s, 3 H), 1.79 - 1.91 (m, 2
H), 1.62 - 1.73 (m, 1 H), 1.30 (q, 3
O H).
6 (delta) (d4 Me0D): 7.02-7.01 (m,
CI 1H), 6.89-6.87 (m, 1H), 3.72-3.70
0
(m, 3H), 2.53-2.51 (m, 1H), 2.37-
A-17 2.30 (m, 1H), 2.04 (s, 3H), 2.00-1.92
o (m, 1H), 1.89-1.76 (m, 2H), 1.20-
1.09 (m, 6H), 1.02 (s, 3H).
6 (delta) 7.12-7.10 (m, 1H), 6.86-
CI 6.82 (m, 1H), 6.01-5.80 (m, 1H),
0
4.11-3.97 (m, 2H), 3.65-3.60 (m,
A-18
2H), 3.37-3.34 (m, 3H), 3.03-2.99
0 (m, 2H), 2.27-1.78 (m, 5H), 2.04 (s,
O 3H), 1.37-1.30 (m, 1H).

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1H NMR data (400 MHz, in 00013
Compound
Structure solvent, unless otherwise stated) or
Number
other physical data
6 (delta) (00300) 7.10 (s, 1H), 6.96-
A-19 6.90 (m, 1H), 4.44-4.36 (m, 2H),
2.96 (br, 2H), 2.22-2.14 (m, 3H),
2.02 (s, 3H), 1.87-1.81 (m, 2H),
1.71-1.67 (m, 1H)
0
6 (delta) 7.12 (s, 1H), 6.84 (s, 1H),
0 CI
6.00 (br s, 1H), 3.72 (s, 3H), 3.70 (m,
A-20 4H), 2.57 (br s, 4H), 2.05 (s, 3H),
o 1.73 (br t, 2H), 1.67 (br t, 2H)
0
6 (delta) (500 MHz) 7.16 (s, 2H),
0 5.38 (br s, 1H), 2.64-2.76 (m, 2H),
A-21 2.56-2.63 (m, 2H), 2.37-2.49 (m,
2H), 2.26 (dd, 1H), 2.13 (s, 3H),
0
2.01-2.07 (m, 9H), 1.76-1.83 (m, 2H)
6 (delta) (500 MHz) 7.12 (d, 1H),
0 CI
6.80-6.89 (m, 1H), 5.74 (br s, 1H),
A-22
3.66-3.78 (m, 3H), 2.69 (br s, 4H),
o 2.00-2.15 (m, 5H)
6 (delta) (500 MHz, 00300) 7.03 (s,
0 1H), 6.90 (d, 1H), 3.73 (d, 3H), 2.59-
A-23 2.68 (m, 4H), 2.33-2.46 (m, 3H),
0 2.13 (d, 3H), 2.04-2.06 (m, 3H), 1.81
0
(quin, 2H)

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1H NMR data (400 MHz, in CDCI3
Compound
Structure solvent, unless otherwise stated) or
Number
other physical data
6 (delta) (500 MHz) 7.26 (s, 1H),
0 7.15 (s, 1H), 2.45-2.81 (m, 4H),
A-24 2.17-2.39 (m, 2H), 1.99-2.11 (m,
12H), 1.66-1.75 (m, 1H), 1.56-1.64
0 (m, 1H), 1.33 (d, 3H)
Cl Cl
6 (delta) (500 MHz, CD30D) 7.09 (m,
0
A-25 1H), 6.95 (m, 1H), 3.72 (d, 3H), 2.95
(br s, 2H), 2.14-2.25 (m, 3H), 1.78-
o 1.90 (m, 2H), 1.68 (m, 1H)
0 CI
A-26
o 0
A-27
o
A-28
o
0
A-29
0
a
A-30

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1H NMR data (400 MHz, in CDCI3
Compound
Structure solvent, unless otherwise stated) or
Number
other physical data
A-31
0 CI
A-32
o
0
0
A-33
0
Cl
0
A-34
0
0
A-35
0
6 (delta) (400 MHz, CDCI3 +1 drop
0 CI
of CD30D) 7.12 (d, 1H), 6.83 (d, 1H),
A-36 3.72 (s, 3H), 2.42 (brs, 4H), 2.05 (s,
0õ 3H), 1.19 (s, 3H), 1.16 (s, 3H)

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1H NMR data (400 MHz, in CDCI3
Compound
Structure solvent,
unless otherwise stated) or
Number
other physical data
CI
0
A-37
0
0
A-38
0
0
CI
0
A-39
0
0
0 CI
A-40
0
I 0
N
0
A-41
0
1H NMR data (400 MHz, in C0CI3
Compound
Structure solvent,
unless otherwise stated) or
Number
other physical data

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1H NMR data (400 MHz, in CDCI3
Compound
Structure solvent, unless otherwise stated) or
Number
other physical data
0 6 (delta) 8.60 (d, 1H), 7.69 (td, 1H),
\ A
7.28 - 7.27 (m, 1H), 7.21 (dd, 1H),
0 0
7.08 (d, 2H), 3.78- 3.74 (m, 1H),
P-1
3.66 (s, 3H), 3.38 (dd, 1H), 3.10 -
(=A-14)
\ 0 3.01 (m, 2H), 2.93 - 2.89 (m, 1H),
2.10 (s, 3H), 2.03 (s, 3H), 1.98 (s,
N
3H).
0 6 (delta) 8.60 (d, 1H), 7.69 (td, 1H),
7.28 - 7.27 (m, 1H), 7.21 (dd, 1H),
7.08 (d, 2H), 3.78 - 3.73 (m, 1H),
P-2
3.33 (dd, 1H), 3.06 (dd, 1H), 2.99 -
(=A-15)
0 2.88 (m, 2H), 2.09 (s, 3H), 2.04 (s,
3H), 1.98 (s, 3H), 1.86 (s, 3H).
N
0
6 (delta) (500 MHz) 7.71(d, 2H),
o c
7.35(d, 2H), 7.03(s, 1H), 6.72(3, 1H),
P-3 a 3.77(dd, 4H), 3.64(s, 3H), 3.07(d,
O 2H), 2.89(d, 2H), 2.67(dd, 2H),
o
2.02(s, 3H), 1.86-1.71(m, 4H).
6 (delta) (500 MHz) 7.11 (s, 2H) 3.97
o (dd, 2H) 3.40 (tdd, 2H) 2.93 (dd, 1H)
s,
o 2.64-2.74 (m, 2H) 2.45 (s, 3H) 2.29-
P-4 2.37(m, 1H) 2.06-2.10 (m, 3H) 2.05
(s, 3H) 2.03 (s, 3H) 1.57-1.71 (m,
4H) 1.39-1.51 (m, 2H) 1.25-1.36 (m,
2H)
6 (delta) (500 MHz) 7.04 (s, 2H)
3.13-3.17 (m, 1H) 3.02 (t, 1H) 2.39
0 0
P-5 I(d, 1H) 2.05-2.29 (m, 3H) 2.04 (s,
3H) 2.02 (s, 3H) 1.95-1.99 (m, 3H)
1.70-1.83 (m, 2H) 0.92 (s, 9H)
0

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1H NMR data (400 MHz, in CDCI3
Compound
Structure
solvent, unless otherwise stated) or
Number
other physical data
o 6 (delta) (500 MHz) 7.15 (s, 1H)
IC 6.70-
6.81 (m, 1H) 4.19-4.28 (m, 2H)
3.23 (dt, 1H) 3.12 (brs, 1H) 2.74-
P-6
2.83 (m, 2H) 2.29-2.42 (m, 1H) 2.05-
o 1-F F 2.29 (m, 3H) 2.04 (s, 3H) 1.70-1.91
(m, 2H) 1.23 (t, 3H)
6 (delta) (500 MHz) 7.03 (s, 1H)
6.75-6.78 (m, 1H) 3.69 (d, 3H) 3.07-
CI
0 0 3.13
(m, 2H) 2.41 (d, 1H) 2.14-2.25
P-7 (m,
2H) 2.03-2.04 (m, 3H) 2.02-2.11
(m, 1H) 1.78-1.91 (m, 1H) 1.71 (dtd,
O o 1H) 1.01 (d, 9H)
It should be noted that certain compounds of the invention may exist as a
mixture of isomers,
including sometimes atropisomers, e.g. as noted above, under the conditions
used to obtain
the 1H NMR data. Where this has occurred, the characterising data are reported
for all
.. isomers present at ambient temperature in the specified solvent. Unless
otherwise stated,
proton (1H) NMR spectra disclosed herein were recorded at ambient temperature.
The following compounds B-1, B-2, B-3 or B-4 are not compounds of formula (I)
according to
the present invention. However, a further, independent, aspect of the
invention provides a
compound which is one of compounds B-1, B-2, B-3 or B-4 or a salt (e.g.
agrochemcially
acceptable salt) thereof:
1H NMR data (400 MHz, in CDCI3
Compound
Structure
solvent, unless otherwise stated) or
Number
other physical data

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1H NMR data (400 MHz, in CDCI3
Compound
Structure solvent, unless otherwise stated) or
Number
other physical data
0C1 6 (delta) (500 MHz) 7.15 (s, 1H),
6.87 (s, 1H), 5.69 (brs, 1H), 3.68 (s,
B-1 3H), 3.64 (t, 4H), 3.07 (s, 1H), 2.55
o (brs, 2H), 2.48 (dd, 2H),1.68 (t, 2H),
Cl
0 6 (delta) (500 MHz) 7.22 (d, 1H),
B 2 6.91-6.97 (m, 1H), 6.03 (brs, 1H),
- 3.74 (s, 3H), 3.09-3.16 (s, 1H), 2.39-
0 2.66 (m, 4H), 2.06-2.16 (m, 2H)
CI
0 6 (delta) (500 MHz, CD30D) 7.10 (m,
B-3 1H), 6.96 (m, 1H), 3.72 (d, 3H), 3.55
(d, 1H), 2.96 (brs, 2H), 2.12-2.26 (m,
0 3H), 1.79-1.91 (m, 2H), 1.68 (m, 1H)
OCI
B-4
0
0

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Compounds of Tables 1 to 27
The compounds of the following Tables 1 to 25 and Tables 26 and 27 also
illustrate the
present invention, and are also particular embodiments of the compounds of
formula (I)
according to the present invention. For the most part, these compounds can
generally be
prepared by methods similar or analogous to those shown in the Examples and/or
in the
process section hereinabove using appropriate starting materials.
Table 1 covers 34 compounds of the following type
X
R
0
R2
0
wherein R1, R2 and X are as defined in Table 1.
Table 1
Compound
R1 R2 X
Number
1.01 methyl hydrogen methyl
1.02 methyl methyl methyl
1.03 methyl chlorine methyl
1.04 methyl methoxy methyl
1.05 methyl ethynyl methyl
1.06 methyl ethyl methyl
1.07 methyl vinyl methyl
1.07A methyl 2-methoxyethoxy methyl
1.07B methyl ethoxy methyl
1.08 chlorine hydrogen methyl
1.09 chlorine chlorine methyl
1.10 chlorine methoxy methyl

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Compound
R1 R2 X
Number
1.11 chlorine ethynyl methyl
1.12 chlorine ethyl methyl
1.13 chlorine vinyl methyl
1.13A chlorine 2-methoxyethoxy methyl
1.13B chlorine ethoxy methyl
1.14 methyl hydrogen chlorine
1.15 methyl methyl chlorine
1.16 methyl chlorine chlorine
1.17 methyl methoxy chlorine
1.18 methyl ethynyl chlorine
1.19 methyl ethyl chlorine
1.20 methyl vinyl chlorine
1.20A methyl 2-methoxyethoxy chlorine
1.20B methyl ethoxy chlorine
1.21 chlorine hydrogen chlorine
1.22 chlorine chlorine chlorine
1.23 chlorine methoxy chlorine
1.24 chlorine ethynyl chlorine
1.25 chlorine ethyl chlorine
1.26 chlorine vinyl chlorine
1.27 chlorine 2-methoxyethoxy chlorine
1.28 chlorine ethoxy Chlorine
Table 2 covers 34 compounds of the following type
X
Ri
0
R2
0
wherein R1, R2 and X are as defined in Table 1. The 34 compounds are compounds
2.01 to
2.07, 2.07A, 2.07B, 2.08 to 2.13, 2.13A, 2.13B, 2.14 to 2.20, 2.20A, 2.20B,
and 2.21 to 2.28.

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Table 3 covers 34 compounds of the following type
X
0R1
R2
0
wherein R1, R2 and X are as defined in Table 1. The 34 compounds are compounds
3.01 to
3.07, 3.07A, 3.07B, 3.08 to 3.13, 3.13A, 3.13B, 3.14 to 3.20, 3.20A, 3.20B,
and 3.21 to 3.28.
Table 4 covers 34 compounds of the following type
Ri
R2
wherein R1, R2 and X are as defined in Table 1. The 34 compounds are compounds
4.01 to
4.07, 4.07A, 4.07B, 4.08 to 4.13, 4.13A, 4.13B, 4.14 to 4.20, 4.20A, 4.20B,
and 4.21 to 4.28.
Table 5 covers 34 compounds of the following type
X
oRi
R2
0
wherein R1, R2 and X are as defined in Table 1. The 34 compounds are compounds
5.01 to
5.07, 5.07A, 5.07B, 5.08 to 5.13, 5.13A, 5.13B, 5.14 to 5.20, 5.20A, 5.20B,
and 5.21 to 5.28.
Table 6 covers 34 compounds of the following type
X
Ri
0
R2
0

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wherein R1, R2 and X are as defined in Table 1. The 34 compounds are compounds
6.01 to
6.07, 6.07A, 6.07B, 6.08 to 6.13, 6.13A, 6.13B, 6.14 to 6.20, 6.20A, 6.20B,
and 6.21 to 6.28.
Table 7 covers 34 compounds of the following type
X
0 R
R2
0
wherein R1, R2 and X are as defined in Table 1. The 34 compounds are compounds
7.01 to
7.07, 7.07A, 7.07B, 7.08 to 7.13, 7.13A, 7.13B, 7.14 to 7.20, 7.20A, 7.20B,
and 7.21 to 7.28.
Table 8 covers 34 compounds of the following type
X
/>-
0 R
R2
0
0
wherein R1, R2 and X are as defined in Table 1. The 34 compounds are compounds
8.01 to
8.07, 8.07A, 8.07B, 8.08 to 8.13, 8.13A, 8.13B, 8.14 to 8.20, 8.20A, 8.20B,
and 8.21 to 8.28.
Table 9 covers 34 compounds of the following type
RI
R2
0
0
Ix
wherein R1, R2 and X are as defined in Table 1. The 34 compounds are compounds
9.01 to
9.07, 9.07A, 9.07B, 9.08 to 9.13, 9.13A, 9.13B, 9.14 to 9.20, 9.20A, 9.20B,
and 9.21 to 9.28.
Table 10 covers 34 compounds of the following type

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X
0 R
0
R2
0
wherein R1, R2 and X are as defined in Table 1. The 34 compounds are named as
compounds 10.01 to 10.07, 10.07A, 10.076, 10.08 to 10.13, 10.13A, 10.136,
10.14 to 10.20,
10.20A, 10.206, and 10.21 to 10.28.
Table 11 covers 34 compounds of the following type
X
0 R
0 R2
0
wherein R1, R2 and X are as defined in Table 1. The 34 compounds are named as
compounds 11.01 to 11.07, 11.07A, 11.076, 11.08 to 11.13, 11.13A, 11.136,
11.14 to 11.20,
11.20A, 11.20B, and 11.21 to 11.28.
Table 12 covers 34 compounds of the following type
X
OR
R2
0
wherein R1, R2 and X are as defined in Table 1. The 34 compounds are named as
compounds 12.01 to 12.07, 12.07A, 12.076, 12.08 to 12.13, 12.13A, 12.136,
12.14 to 12.20,
12.20A, 12.206, and 12.21 to 12.28.
Table 13 covers 34 compounds of the following type

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S6'"
X
0 R
R2
0
wherein R1, R2 and X are as defined in Table 1. The 34 compounds are named as
compounds 13.01 to 13.07, 13.07A, 13.0713, 13.08 to 13.13, 13.13A, 13.13B,
13.14 to 13.20,
13.20A, 13.20B, and 13.21 to 13.28.
Table 14 covers 34 compounds of the following type
X
Ri
0
R2
0
wherein R1, R2 and X are as defined in Table 1. The 34 compounds are named as
compounds 14.01 to 14.07, 14.07A, 14.07B, 14.08 to 14.13, 14.13A, 14.1313,
14.14 to 14.20,
14.20A, 14.20B, and 14.21 to 14.28.
Table 15 covers 34 compounds of the following type
X
OR1
R2
0
wherein R1, R2 and X are as defined in Table 1. The 34 compounds are named as
compounds 15.01 to 15.07, 15.07A, 15.0713, 15.08 to 15.13, 15.13A, 15.1313,
15.14 to 15.20,
15.20A, 15.20B, and 15.21 to 15.28.
Table 16 covers 34 compounds of the following type

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X
OR
R2
0
wherein R1, R2 and X are as defined in Table 1. The 34 compounds are named as
compounds 16.01 to 16.07, 16.07A, 16.0713, 16.08 to 16.13, 16.13A, 16.1313,
16.14 to 16.20,
16.20A, 16.20B, and 16.21 to 16.28.
Table 17 covers 34 compounds of the following type
X
OR
0 R2
0
wherein R1, R2 and X are as defined in Table 1. The 34 compounds are named as
compounds 17.01 to 17.07, 17.07A, 17.0713, 17.08 to 17.13, 17.13A, 17.1313,
17.14 to 17.20,
17.20A, 17.20B, and 17.21 to 17.28.
Table 18 covers 34 compounds of the following type
X
R
0
0 R2
wherein R1, R2 and X are as defined in Table 1. The 34 compounds are named as
compounds 18.01 to 18.07, 18.07A, 18.0713, 18.08 to 18.13, 18.13A, 18.13B,
18.14 to 18.20,
18.20A, 18.20B, and 18.21 to 18.28.
Table 19 covers 34 compounds of the following type

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X
R
0
O R2
wherein R1, R2 and X are as defined in Table 1. The 34 compounds are named as
compounds 19.01 to 19.07, 19.07A, 19.076, 19.08 to 19.13, 19.13A, 19.136,
19.14 to 19.20,
19.20A, 19.20B, and 19.21 to 19.28.
Table 20 covers 34 compounds of the following type
X
oR1
O R2
0
wherein R1, R2 and X are as defined in Table 1. The 34 compounds are named as
compounds 20.01 to 20.07, 20.07A, 20.076, 20.08 to 20.13, 20.13A, 20.136,
20.14 to 20.20,
20.20A, 20.206, and 20.21 to 20.28.
Table 21 covers 34 compounds of the following type
X
Ri
0
O R2
0
0
wherein R1, R2 and X are as defined in Table 1. The 34 compounds are named as
compounds 21.01 to 21.07, 21.07A, 21.07B, 21.08 to 21.13, 21.13A, 21.136,
21.14 to 21.20,
21.20A, 21.206, and 21.21 to 21.28.
Table 22 covers 34 compounds of the following type

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X
0R1 el
0 R2
0
wherein R1, R2 and X are as defined in Table 1. The 34 compounds are named as
compounds 22.01 to 22.07, 22.07A, 22.07B, 22.08 to 22.13, 22.13A, 22.13B,
22.14 to 22.20,
22.20A, 22.20B, and 22.21 to 22.28.
Table 23 covers 34 compounds of the following type
X
OR el
0 R2
0
wherein R1, R2 and X are as defined in Table 1. The 34 compounds are named as
compounds 23.01 to 23.07, 23.07A, 23.07B, 23.08 to 23.13, 23.13A, 23.13B,
23.14 to 23.20,
23.20A, 23.20B, and 23.21 to 23.28.
Table 24 covers 34 compounds of the following type
X
oRi
o
R2
0
wherein R1, R2 and X are as defined in Table 1. The 34 compounds are named as
compounds 24.01 to 24.07, 24.07A, 24.07B, 24.08 to 24.13, 24.13A, 24.13B,
24.14 to 24.20,
24.20A, 24.20B, and 24.21 to 24.28.
Table 25 covers 34 compounds of the following type

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X
0 R
R2
I 0
N
wherein R1, R2 and X are as defined in Table 1. The 34 compounds are named as
compounds 25.01 to 25.07, 25.07A, 25.07B, 25.08 to 25.13, 25.13A, 25.13B,
25.14 to 25.20,
25.20A, 25.20B, and 25.21 to 25.28.
Table 26 covers 34 compounds of the following type
X
R /;=
0
R2
0
wherein R1, R2 and X are as defined in Table 1. The 34 compounds are named as
compounds 26.01 to 26.07, 26.07A, 26.07B, 26.08 to 26.13, 26.13A, 26.13B,
26.14 to 26.20,
26.20A, 26.20B, and 26.21 to 26.28.
Table 27 covers 34 compounds of the following type
X
Ri
0
R2
0
wherein R1, R2 and X are as defined in Table 1. The 34 compounds are named as
compounds 27.01 to 27.07, 27.07A, 27.07B, 27.08 to 27.13, 27.13A, 27.13B,
27.14 to 27.20,
27.20A, 27.20B, and 27.21 to 27.28.

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BIOLOGICAL EXAMPLES
BIOLOGICAL EXAMPLE 1A
Test 1A ¨ Glasshouse assay for herbicidal activity
Seeds of a variety of test species were sown in standard soil in pots. After
cultivation for one
day (pre-emergence) or after 8 days cultivation (post-emergence) under
controlled conditions
in a glasshouse (at 24/16 C, day/night; 14 hours light; 65 % humidity), the
plants were
sprayed with an aqueous spray solution derived from the formulation of the
technical active
TM
ingredient in acetone / water (50:50) solution containing 0.5% Tween 20
(polyoxyethelyene
sorbitan monolaurate, CAS RN 9005-64-5). The test plants were then grown in a
glasshouse
under controlled conditions in a glasshouse (at 24/16 C, day/night; 14 hours
light; 65%
humidity) and watered twice daily. After 13 days for pre and post-emergence,
the test was
evaluated visually for percentage phytotoxicity to the plant (where 100 =
total damage to
plant; 0 = no damage to plant).
Biological Example 1A - Pre-Emergence Herbicidal Activity
Test plants:
Alopecurus myosuroides (ALOMY), Setaria faberi (SETFA), Echinochloa crus-galli
(ECHCG),
Solanum nigrum (SOLNI), Amaranthus retroflexus (AMARE), 1pomoea hederacea
(IPOHE),
and Abutilon theophasti Medik. (ABUTH, common English name "velvetleaf"). Of
these,
Alopecurus myosuroides (ALOMY), Setaria faberi (SETFA), and Echinochloa crus-
galli
(ECHCG) are grassy monocotyledonous weeds.
Compound Appli-
Lu < >- 0 w i
Number ca- 2
_1
< u_
2
0 0
i I
0 H
H
D
0 2 Lu 0
tion Cf) < CO .7L1 W _ <
Rate
g/ ha
A-1 250 0 0 90 90 80 0 -
A-2 250 0 0 70 90 100 10 -
Date Recue/Date Received 2020-05-25

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A-3 250 0 0 100 100 100 40 -
A-4 250 0 0 70 100 100 0 -
A-5 250 - 0 90 100 100 - 0
A-6 250 20 30 100 100 100 10 -
A-7 250 40 60 30 80 80 20 -
A-8 250 70 90 90 90 100 30 -
A-9 250 70 100 100 100 100 20 -
A-10 250 - 0 100 100 100 - 0
A-11 250 - 70 80 100 100 - 50
A-12 250 - 0 100 100 100 - 0
A-12 62.5 - 0 100 90 90 - 0
Reference 250 - 0 100 70 90 - 0
(Comparator)
Compound X-4
Reference 30 - 0 40 0 30 - 0
(Comparator)
Compound X-4
A-13 (compound 250 - 80 100 100 100 70
of the invention,
to be compared
with X-4 above)
A-13 (compound 30 - 100 70 70 100 - 30
of the invention,
to be compared
with X-4 above)

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A-14 (= P-1) 250 - 70 100 100 100 - 70
A-15 (= P-2) 250 - 40 100 100 100 - 50
A-16 250 - 80 100 100 100 - 70
A-17 250 - 60 90 90 100 - 70
A-19 250 - 0 60 40 60 - 0
A-20 250 - 90 100 100 100 - 80
A-21 250 - 90 100 100 100 - 10
A-22 250 - 70 100 90 100 - 60
A-23 250 - 70 90 90 100 - 30
A-24 250 - 80 100 90 100 - 20
P-3 250 - 100 100 100 100 - 80
P-4 250 - 20 80 80 100 - 10
P-5 250 - 0 100 100 100 - 0
P-6 250 - 20 10 10 - 0
P-7 250 - 0 100 100 100 - 0
B-1 250 - 20 80 90 100 - 0
B-2 250 - 10 90 60 90 - 10
B-3 250 - 90 100 80 90 - 100
B-4 250 - 40 70 100 100 - 10

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Compound Appli-
in < >- 0 wI
Number ca- _,2 f: u_ 2 0 I H
< 1¨ 0 i 0 D
0 2 Lu _11 0 o_ co
tion Cl) < u) < LE ¨ <
Rate
g/ ha
Note: a hyphen (-) in the table above indicates that no measurement was made.
Biological Example 1A - Post-Emergence Herbicidal Activity
Test plants:
Alopecurus myosuroides (ALOMY), Setaria faberi (SETFA), Echinochloa crus-galli
(ECHCG),
Solanum nigrum (SOLNI), Amaranthus retroflexus (AMARE), 1pomoea hederacea
(IPOHE),
and Abutilon theophasti Medik. (ABUTH, common English name "velvetleaf"). Of
these,
Alopecurus myosuroides (ALOMY), Setaria faberi (SETFA), and Echinochloa crus-
galli
(ECHCG) are grassy monocotyledonous weeds.
Compound Appli- 2 i-ki >- 0 w i
0 i !¨
Number cation 51 `4 ILI 0 i 0 P
Lu a cci
¨ <
Rate
g / ha
A-1 250 30 10 70 90 100 90 -
A-2 250 20 0 100 90 100 30 -
A-3 250 20 10 90 90 100 0 -
A-4 250 0 0 80 90 100 0 -
A-5 250 - 0 100 100 100 - 60
A-5 30 - 10 70 80 100 - 0

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A-6 250 20 0 90 70 100 20 -
A-6 62.5 20 10 90 70 100 30 -
A-7 250 50 0 80 80 80 20 -
A-8 250 80 40 90 80 100 70 -
A-9 250 80 30 90 100 100 50 -
A-10 250 - 50 100 100 100 - 80
A-11 250 - 30 100 100 100 - 80
A-12 250 - 0 to 100 90 to 100 - 50t0
100 60
A-12 62.5 - 0 100 80 100 - 0
Reference (Comparator) 250 - 0 100 80 100 - 80
Compound X-4
Reference (Comparator) 30 - 0 50 60 40 0
Compound X-4
A-13 (compound of the 250 - 60 100 100 100 80
invention, to be compared
with X-4 above)
A-13 (compound of the 30 - 30 90 70 80 - 40
invention, to be compared
with X-4 above)
A-14 (= P-1) 250 - 20 100 100 100 - 80
A-15 (= P-2) 250 - 60 100 100 100 - 80
A-15 30 - 0 100 90 100 - 20
A-16 250 - 70 100 100 100 - 60

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A-16 30 - 30 100 90 100 - 60
A-17 250 - 0 90 90 100 - 10
A-19 250 - 0 90 70 100 - 0
A-20 250 - 80 100 100 100 - 80
A-20 30 - 80 100 100 100 - 80
A-20 8 - 10 90 90 100 - 50
A-21 250 - 20 100 90 100 - 60
A-21 30 - 80 70 50 80 - 10
A-22 250 - 0 100 90 100 - 70
A-22 30 - 20 80 60 90 - 10
A-23 250 - 20 100 90 100 - 70
A-23 30 - 10 100 60 100 - 30
A-24 250 - 60 100 100 100 - 60
A-24 30 - 0 100 90 100 0
P-3 250 - 80 100 90 100 - 80
P-3 30 - 80 100 100 100 - 70
P-3 8 - 20 100 90 100 - 20
P-4 250 - 0 80 80 80 - 0
P-5 250 - 10 90 90 100 - 70

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P-5 30 - 0 70 60 80 - 0
P-6 250 - 20 50 50 80 - 0
P-7 250 - 0 100 100 100 - 70
P-7 30 - 0 90 90 100 - 10
B-1 250 - 0 100 100 100 - 60
B-2 250 - 0 90 70 100 - 0
B-3 250 - 0 90 80 100 - 0
B-4 250 - 30 90 100 100 - 70
Compound Appli-
LLJ < - 0 w 1
Number ca- _,2 r: LL 2 0 I H
H 0 1 0 D
ion cµ..) 2 Li j 0 0_ mCl)< u) .7t1 w ¨ <
Rate
g/ ha
Note: a hyphen (-) in the table above indicates that no measurement was made.

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BIOLOGICAL EXAMPLE 1B
Test 1B ¨ Glasshouse assay for herbicidal activity
Seeds of a variety of monocotyledonous and dicotyledonous test plants are sown
in standard
soil in pots. The plants are cultivated for one day (for pre-emergence) or for
about 12 days
(range = 10-13 days) (for post-emergence) under controlled conditions in a
glasshouse
(warm climate species at 24/18 C, cool climate species at 20/16 C, both at
day/night; 16
hours light; 65 % humidity).
An "instant formulation", known as the "IF50", containing 50 g/litre (i.e. 5%
w/v) of the
"technical" (i.e. unformulated) active ingredient is prepared by dissolving
the active ingredient
in a mixture of organic solvents and emulsifier, details of which are provided
in the Table
below. This 1F50 is then mixed with a small, variable amount of acetone to aid
dissolution,
before addition of a 0.2% v/v aqueous solution of the adjuvant X-77 (which is
a mixture of
alkyl aryl polyoxyethylene glycols and free fatty acids in isopropanol, CAS
Registry number
11097-66-8), as the aqueous diluent, to form an aqueous spray solution which
contains a
predetermined concentration of the active ingredient (which varies depending
on the
application rate of the active ingredient to the plants) and 0.2% v/v of the
adjuvant X-77. This
aqueous spray solution is then sprayed onto the plants, after one day's
cultivation (for pre-
emergence) or after about 12 days' cultivation (for post-emergence).
Table: Composition of the mixture of organic solvents and emulsifier used as a
base for the
instant formulation (IF50).
_______________________________________________________________
Component Supplier Chemical description CAS Amount /
Registry %w/w
number
Emulsogen EL360 TM Clariant castor oil ethoxylate 61791-12-6 11.12
(as emulsifier)
N-methylpyrrolidone widely 1-methy1-2-pyrrolidone 872-50-4 44.44
available
Dowanol DPM TM Dow dipropylene glycol 34590-94-8 44.44
glycol ether monomethyl ether
The test plants are then grown on, in a glasshouse (greenhouse) under
controlled conditions

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(at either 24/18 C or 20/16 C (day/night) as mentioned above; 16 hours light;
65% humidity)
and are watered twice daily. Either 15 days after application of the herbicide
(15 DAA) (for
post-emergence), or 20 days after application of the herbicide (20 DAA) (for
pre-emergence),
the test plants are evaluated visually, and an assessed percentage
phytotoxicity score is
given for each herbicidal application on each plant species (where 100% =
total damage to
plant; 0% = no damage to plant).
Some of the test plants are as follows:
Cool climate crop plants: Triticum aestivum (TRZAW, winter wheat), Brassica
napus
(BRSNN, rape, also called oilseed rape or rapeseed), Beta vulgaris (BEAVA,
sugar beet).
Warm climate crop plants: Glycine max (GLXMA, soybean).
Cool climate ("cool season") grassy monocotyledonous weeds: Alopecurus
myosuroides
(ALOMY), Avena fatua (AVEFA), Lolium perenne (LOLPE).
Warm climate ("warm season") grassy monocotyledonous weeds: Setaria faberi
(SETFA),
SORVU (Sorghum bicolor (L.) Moench ssp. Bicolor, or Sorghum vulgare Pers.),
Digitaria
sanguinalis (Dl GSA), Echinochloa crus-galli (ECHCG), and Brachiaria
plantaginea (BRAPL).
Biological Example 1B - Pre-Emergence Herbicidal Activity
< z < >- < w < D < 0 _1
Compound Appl. () <>t' c(-3 C2
Number Rate E = cu, ; 5
(g/ha)
A-1 500 40 10 60 10 70 10 100 50 60 60 100 90
g/ha
A-2 500 60 0 40 0 100 80 100 90 80 100 100 100
g/ha
A-5 500 20 0 90 0 80 40 100 90 90 100 100 100
g/ha
A-6 125 10 0 70 0 60 40 80 80 80 100 60 80
g/ha
A-9 125 20 10 80 20 80 80 100 100 90 100 90 -
g/ha
A-10 125 20 0 0 0 80 60 100 80 80 90 90 80
g/ha
A-12 250 30 40 20 10 60 50 100 100 90 100 100 100
g/ha

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A-13 250 20 20
70 10 80 30 100 80 80 100 90 90
g/ha
A-14 250 40 20
60 30 80 70 100 90 BO 100 80 90
(= P-1) g/ha
A-15 125 0 10 80
0 80 50 90 80 80 100 80 90
(= P-2) g/ha
A-16 250 0 20 0 0 50 40 70 90 80 100 80 -
g/ha
A-17 250 0 10 0
0 0 60 50 50 50 100 100 -
g/ha
Note: A hyphen (-) in the table above indicates that no measurement was made.
Biological Example 1B - Post-Emergence Herbicidal Activity
< z < >- < w < < 0 -I
Compound Appl. () F) E h j- r ce, c<lt-
Number Rate ;-, 2 5
(g/ha)
A-1 60 80 70 70 30 80 60 80 70 0 80 90 90
g/ha
A-2 60 80 40 70 10 90 80 80 100 80 100 100 100
g/ha
A-5 500 80 40 80 30 90 80 80 100 100 100 100 100
g/ha
A-5 125 70 30 80 30 80 80 80 100 100 100 100 100
g/ha
A-5 60 30 20 70 40 80 30 70 90 80 100 100 100
g/ha
A-5 30 30 10 70 40 70 30 30 80 70 90 100 90
g/ha
A-6 60 40 0 60 50 50 60 70 100 90 100 90 100
g/ha
A-6 30 - 0 40 40 50 50 40 100 90 100 90 90
g/ha
A-8 30 50 50 70 30 80 70 40 90 90 100 100 90
g/ha

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A-9 30 60 60 50
0 80 70 60 90 80 100 100 -
g/h a
A-10 125 80 20 60 20 100 40 80 100 100 100 100 100
g/ha
A-10 30 60 10 40 20 60 20 30 80 100 90 90 90
g/h a
A-12 125 60 10 80 20 70 30 70 80 100 100 100 100
g/h a
A-12 30 40 0 60 0 10 0 0 70 80 100 90 70
g/h a
A-13 125 30 60 70 20 30 20 70 80 80 80 80 100
g/h a
A-14 125 80 70
70 40 80 60 80 90 100 100 100 100
(= P-1) g/ha
A-14 30 60 40 60
30 70 20 70 80 80 80 80 70
(= P-1) g/ha
A-15 125 80 60
70 30 80 80 90 100 100 100 100 100
(= P-2) g/ha
A-15 30 70 20 60
30 70 60 80 80 80 90 80 100
(= P-2) g/ha
A-16 125 60 30 50 0 80 60 70 100 100 100 100 -
g/h a
A-16 30 10 0 10 0 20 0 20 80 80 80 80 -
g/h a
A-17 250 10 10 10 10 50 0 20 80 80 70 90 -
g/h a
A-18 250 10 20
30 30 0 20 0 80 100 90 90 70
g/h a
Comparator 125 0 0 20 - 40 0 40 80 - 80 60 80
compound g/ha
X-9
Comparator 60 0 0 0 - 20 0 0 80 - 70 40 80
compound g/ha
X-9

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Comparator 60 20 0 0 - 80 50 70 100 - 100 70 90
compound g/ha
X-10
Compound Appl. z < >- < w < D < 0
Number Rate N X (i)
I¨ 0 120 < < U) w(g/
ha)
Note: A hyphen (-) in the table above indicates that no measurement was made.
0
rV
Note: Compound A-5 has the following structure:
0
0
Comparator compound X-9 is
0
0
Comparator compound X-10 is ;
this is compound 21.115 disclosed on
page 105 of WO 01/17972 A2. Comparator compound X-10 appears at first sight to
have a
lower post-emergence activity on ECHCG (at 60 g/ha) than Compound A-5 of the
present
invention.
Note: The herbicidal activity data (e.g. post-emergence) shown above in
Biological Example
1B for Comparator compounds X-9 and X-10 is thought likely to have been
measured some
years ago, probably using a variant of the above-described test method. Also,
for the post-
emergence activity of X-9 and X-10 it is not currently known exactly how many
days after
application of the herbicide the phytotoxicity on the plants was measured.

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BIOLOGICAL EXAMPLE 2 ¨ Comparative herbicidal data
Comparative herbicidal data is given below for certain exemplified compounds
with 4-(prop-
1-yny1)-2,6-dimethylphenyl or 4-(chloroethynyI)-2,6-dimethylphenyl headgroups,
compared to
the corresponding compounds with either 4-ethyny1-2,6-dimethylphenyl or 2,4,6-
trimethylphenyl headgroups, as follows. Comparative herbicidal data is also
given below for
certain exemplified compounds with 4-(prop-1-ynyI)-2-chloro-6-methoxyphenyl
headgroups,
compared to the corresponding compounds with 4-ethyny1-2-chloro-6-
methoxyphenyl or
4-(but-1-ynyI)-2-chloro-6-methoxyphenyl or 4-methyl-2-chloro-6-methoxyphenyl
or 2-chloro-
6-methoxyphenyl headgroups, as follows.
Except where specified otherwise, the glasshouse screen for herbicidal
activity is
substantially the same as that presented in Biological Example 1A (Test 1A)
hereinabove.
The weed abbreviations are as defined in Biological Example 1A.
Biological Example 2: Post-Emergence Herbicidal Activity (comparative data)
Table B2(A) - Post-emergence herbicidal activities (percentage phytotoxicity)
at 62.5 g/ha
application rate are as follows:
Comp- LOLPE ALOMY ECHCG AVEFA SETFA
ound Structure
no.
not 80 90 not 40
IIIi 0 tested tested
A-1
0
0
CI
not 50 60 not 60
0 tested tested
A-7
0
0

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o /
not 10 0 not 30
Compar
tested tested
-ative
example
0
X-1 0
Cl
not 70 100 not 90
0 tested tested
A-6
not 10 70 not 60
Compar 0
-ative tested tested
example
X-2 0
-y- -
not 80 100 not 90
¨
A-8 tested tested
o
'ci
0
not 90 100 not 90
0
tested tested
A-9
0
Compar 0 not 60 50 not 70
-ative 0 tested tested
example 0
X-3
0
0
0
Note: Comparative example compound X-3 ( ) is disclosed as
compound 13.041 within Table 13 on page 78 of WO 2010/046194 Al (Syngenta
Limited),
after cross-referencing to the phenyl substituents disclosed in compound 1.041
in Table 1 on
pages 67-69 of of WO 2010/046194 Al.

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Table B2(B) - Post-emergence herbicidal activities (percentage phytotoxicity)
at 15.625
g/ha application rate are as follows:
Comp- LOLPE ALOMY ECHCG AVEFA SETFA
ound Structure
no.
not 10 20 not 20
0 tested tested
A-1
0
0
a
not 30 0 not 40
0 tested tested
A-7
0
0
not 20 0 not 0
Cornpar 0
tested tested
-ative
example
0
X-1 0
CI
not 70 90 not 90
0 tested tested
A-6
0
not 0 0 not 50
Compar 0
tested tested
-ative
example
X-2 0
0
I I not 70 90 not 80
A-8 tested tested
0 %-=
'ci

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0
not 80 100 not 80
0
A-9
tested tested
0
Compar 0 not 30 20 not 60
-ative 0 tested tested
example 0
X-3
0
0
0
Note: Comparative example compound X-3 ( ) is disclosed as
compound 13.041 within Table 13 on page 78 of WO 2010/046194 Al (Syngenta
Limited),
after cross-referencing to the phenyl substituents disclosed in compound 1.041
in Table 1 on
pages 67-69 of of WO 2010/046194 Al.
Table B2(C) - Post-emergence herbicidal activities (percentage phytotoxicity)
at 30 g/ha
application rate are as follows:
Test plants: Alopecurus myosuroides (ALOMY), Setaria faberi (SETFA),
Echinochloa crus-
gaffi (ECHCG), Amaranthus retroflexus (AMARE), and Abutilon theophasti Medik.
(ABUTH,
common English name "velvetleaf"). Of these, Alopecurus myosuroides (ALOMY),
Setaria
faberi (SETFA), and Echinochloa crus-gaffi (ECHCG) are grassy monocotyledonous
weeds.
Comp-
Structure AMARE SETFA ALOMY ECHCG ABUTH
ound no.
0
A-5 10 70 80 100 0
0

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./>
CI
0
A-12 0 90 90 100 40
0
0
C
0I
B-3 0 60 30 70 0
o 0
0CI
B-4 20 70 60 80 0
0
Reference
(Comp- 0
arator)
30 60 30 80 10
Com-
o 0,,
pound
X-5
0 -------
A-13 30 90 70 80 40
N
HCI
Reference
0
(Comp-
arator)
0 0 50 60 40 0
Com-
pound 2N FoH
X-4

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o CI
A-20 80 100 100 100 80
o
o CI
B-1 0 70 70 80 10
o 0
0
Reference
o CI
(Comp-
arator)
20 10 20 10 0
Com-
pound 0
X-6
o CI
A-22 20 80 60 90 10
o 0
CI
0
B-2 0 70 0 80 0
LL
0
A-21 80 70 50 80 10
0
Reference
(Comp-
arator)
0 20 30 10 0
Com-
pound
X-7

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o
A-24 0 100 90 100 0
s
Reference
(Comp-
Co 0
arator)
0 80 70 70 0
m-
pound
X-8
Comp-
Structure AMARE SETFA ALOMY ECHCG ABUTH
ound no.
0
Note: Reference (Comparator) Compounds X-7 ( s 0 ) and X-8 (
Iw
) are disclosed as compounds 112 and T18 respectively on page
47 of WO 2008/110308 Al (Syngenta Participations AG).
Table B2(D) - Post-emergence herbicidal activities (percentage phytotoxicity)
at 8 g/ha
application rate are as follows:
Comp- AMARE SETFA ALOMY ECHCG ABUTH
Structure
ound no.
0
A-5 0 30 50 80 0
0

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0C1
A-12 0 50 40 90 10
0
CI
0
B-3 0 20 0 20 0
0
0
Reference
(Comp- 0
arator)
30 20 0 0 0
Com-
o 0
pound
X-5
9
A-13 0 80 60 80 0
HCI
Reference
0 =r-
(Comp-
arator)
0 0 40 40 20 0
Com-
pound
X-4
0 CI
A-20 10 90 90 100 50
o

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//-
0 CI
B-1 0 30 10 20 0
o 0
0
0 CI
A-22 0 70 10 80
o 0
CI
0
B-2 0 10 0 0 0
0
9
A-21 30 50 50 80 70
Reference
(Comp-
arator)
0 0 0 0
Com-
pound
X-7
Cornp-
Structure AMARE SETFA ALOMY ECHCG ABUTH
ound no.
0
Note: Reference (Comparator) Compound X-7 ( s ) is disclosed as
compound T12 on page 47 of WO 2008/110308 Al (Syngenta Participations AG).

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BIOLOGICAL EXAMPLE 3
Assay for Biological Example 3 ¨ Glasshouse assay for herbicidal activity,
using
various adjuvant systems
Materials and Methods
Herbicide Application: Post-emergence foliar spray application, 200 L/ha,
usually one or
two replicates for the weeds (depending on application rate), and two
replicates for soybean.
Climate: Standard warm conditions (tropical), in glasshouse. Specifically,
the
glasshouse bay conditions are 24 C / 18 C day/night; 16/8 hours light/dark;
65% humidity.
Plants: The herbicidal application takes place at the following growth stages
for plants
which include inter alia one or more of the following plants (usually the
herbicidal application
takes place on at least the following six plants: DIGSA, ELFIN, SETFA, GLXMA
Nikko, and
GLXMA TMG133, and either BRADC or BRAPP):
Brachiaria decumbens (BRADC) ¨ growth stage (GS) 12 or 13 (or GS 12) ¨ or, if
BRADC is
not used, then Brachiaria platyphylla (BRAPP) ¨ growth stage 12 or 13
Digitaria sanguinalis (DIGSA) ¨ growth stage 12 or 13
Eleusine indica (ELFIN) ¨ growth stage 12 or 13
Setaria faberi (SETFA) ¨ growth stage 12 or 13
Echinochloa crus-galli (ECHCG) ¨ growth stage 12 or 13
Sorghum halepense (annual) (SORHA) ¨ growth stage 12 or 13
Panicum dichotomiflorum (PANDI) ¨ growth stage 12 or 13
Glycine max (GLXMA, soybean) cultivar "Nikko" ¨ growth stage: 1st trifoliate
Glycine max (GLXMA, soybean) cultivar "TMG133" ¨which is Roundup Ready TM
glyphosate-tolerant soybean cultivar TMG133 (typically available from Monsanto
in Brazil) ¨
growth stage: 1st trifoliate.
Herbicidal compositions tested:
Each test Compound is applied with one of the following adjuvant systems (all
percentages
are final concentrations in the aqueous spray mixture):
Adjuvant system 1: 0.5% v/v Adigor TM *, 1.0% v/v AMS (ammonium sulphate) and
12.5%
v/v IPA (isopropyl alcohol).
Adjuvant system 2: 0.5% v/v Adigor TM * and 12.5% v/v IPA (isopropyl alcohol).

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Adjuvant system 3: 0.5% v/v Hexamoll TM DINCH **, 1.0% v/v AMS (ammonium
sulphate)
and 12.5% v/v IPA (isopropyl alcohol).
*Adigor TM (currently available in many countries from Syngenta) is an
emulsifiable
concentrate which consists of:
(i) ethoxylated alcohols, which typically includes ethoxylated higher alcohols
(e.g. ethoxylates
of alcohols wherein the alcohols are within the range of C12-C22); and
(ii) a mixture of heavy aromatic hydrocarbons, which typically includes (e.g.
includes 50% or
more by weight of the heavy aromatic hydrocarbons of) a mixture of
naphthalenes each of
which is substituted by one or more alkyls wherein the alkyl(s) in total have
1-4 carbon atoms
per naphthalene molecule (e.g. Solvesso 200 ND TM); and
(iii) about 47% w/w and/or about 45% w/v (with respect to the emulsifiable
concentrate) of
methylated rapeseed oil (rapeseed oil methyl ester) (e.g. Agnique ME 18 RD-F
TM), as an
adjuvant.
** Hexamoll TM DINCH TM is 1,2-cyclohexane dicarboxylic acid di-isononyl ester
(
0
cX ,,[iso-C9H19]
0
0,,
[iso-C9H19]
0 , CAS
Registry no. 166412-78-8), and is usually available from
BASF. "Isononyl" in this context is thought to mean a mixture of two or more
branched
isomers of C9H19.
Method:
Seeds of the weed plants, typically including inter alia [either Brachiaria
decumbens
(BRADC) or Brachiaria platyphylla (BRAPP)], Digitaria sanguinalis (DIGSA),
Eleusine indica
(ELEIN), Setaria faberi (SETFA) are sown in seed trays (troughs) containing
clay loam soil
(pH 7.0, 2.2% organic matter, "Trough Mix A"); and soybean seed is sown in
pots containing
the same soil with 3 soybean seedlings per pot. The plants are sprayed with
the test
herbicide when they reach the growth stages mentioned above.
The test herbicidal solutions are prepared by mixing the appropriate aliquots
of the test
substance(s) and the adjuvant system indicated above *** in deionised water to
give the
desired treatment concentration.
The herbicidal application is made as a foliar spray, using a tracksprayer.
Following the
herbicidal application, the plants are watered twice per day for the duration
of the test.

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A visual assessment of the A) herbicidal damage is made 7 and 14 Days After
herbicide
Application (DAA) (or, in a minority of cases, 7 and 15 DAA), and the results
are recorded as
% visual herbicidal damage where 0% = no damage to plants and 100% = plant
totally killed.
***Adjuvant system = either Adigor TM or Hexamoll DINCH TM at 0.5% v/v, and
12.5% v/v IPA
(isopropyl alcohol), and in most cases also 1.0% v/v AMS (ammonium sulphate);
all
percentages are final concentrations in the aqueous spray mixture.
Biological Example 3 - Post-Emergence Activity - Results at 14 or 15 Days
After
herbicide Application
Compounds A-5, A-6, A-10, A-12, A-16, A-20, A-21, A-22, A-23 and A-25, which
are
compounds of formula (I) according to the present invention, and compound B-1,
were tested
in a test method substantially as described above.
Compounds A-5 and A-10 were tested using the 0.5% v/v Adigor TM + 12.5% v/v
IPA
adjuvant system. Compounds A-6, A-12, A-20, A-21, A-22, A-23, A-25 and B-1
were tested
using the 0.5% v/v Adigor TM + 1.0% v/v AMS + 12.5% v/v IPA adjuvant system.
Compound
A-16 was tested using the 0.5% v/v Hexamol Dinch TM + 1.0% v/v AMS + 12.5% v/v
IPA
adjuvant system.
The percentages of herbicidal damage / plant control, at 14 Days After
herbicide Application
(DAA) (or, in a minority of cases, at 15 DAA), for the Compounds tested and
for some of the
plants tested, were in the following percentage ranges.
Control of Brachiaria decumbens (BRADC) or Brachiaria platyphyfia (BRAPP),
both warm-
climate (warm-season) grassy weeds
At 14 or 15 DAA, certain test compounds (Compound A-12, A-16, A-22 or A-23)
showed
percentage control of (percentage phytotoxicities on) Brachiaria decumbens
(BRADC) in the
range of from 80% to 95%, when applied post-emergence at an application rate
of 8g/ha.

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At 14 DAR, certain test compounds (Compound A-5 or A-10) showed percentage
control of
Brachiaria decumbens (BRADC) in the range of from 65% to 75%, when applied
post-
emergence at an application rate of 8g/ha.
At 15 DAA, certain test compounds (Compound A-21 or B-1) showed percentage
control of
Brachiaria decumbens (BRADC) in the range of from 50% to 55%, when applied
post-
emergence at an application rate of 8g/ha.
At 14 DAA, Compound A-25 showed percentage control of Brachiaria decumbens
(BRADC)
of 15%, when applied post-emergence at an application rate of 8g/ha.
At 14 DAA, certain test compounds (Compound A-6 or A-20) showed percentage
control of
Brachiaria platyphylla (BRAPP) in the range of from 95% to 100%, when applied
post-
emergence at an application rate of 8g/ha.
Control of Digitaria sanguinalis (DIGSA), a warm-climate (warm-season) grassy
weed
At 14 or 15 DAA, certain test compounds (Compound A-5, A-6, A-10, A-12, A-16,
A-21, A-22
or A-23) showed percentage control of (percentage phytotoxicities on)
Digitaria sanguinalis
(DIGSA) in the range of from 85% to 95%, when applied post-emergence at an
application
rate of 8g/ha.
At 14 DAR, Compound A-20 showed a percentage control of Digitaria sanguinalis
(DIGSA) of
100%, when applied post-emergence at an application rate of 8g/ha.
At 15 DAA, Compound B-1 showed a percentage control of Digitaria sanguinalis
(DIGSA) of
85%, when applied post-emergence at an application rate of 8g/ha.
At 14 DAR, Compound A-25 showed a percentage control of Digitaria sanguinalis
(DIGSA) of
60%, when applied post-emergence at an application rate of 8g/ha.
Control of Eleusine indica (ELEIN), a warm-climate (warm-season) grassy weed
At 14 or 15 DAA, certain test compounds (Compound A-6, A-10, A-12, A-16, A-21,
A-22, or
A-23) showed percentage control of (percentage phytotoxicities on) Eleusine
indica (ELEIN)

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in the range of from 80% to 99%, when applied post-emergence at an application
rate of
8g/ha.
At 14 DAR, Compound A-5 showed a percentage control of Eleusine indica (ELFIN)
of 45%,
when applied post-emergence at an application rate of 8g/ha.
At 14 DAA, Compound A-20 showed a percentage control of Eleusine indica
(ELEIN) of
95%, when applied post-emergence at an application rate of 8g/ha.
At 15 DAR, Compound B-1 showed a percentage control of Eleusine indica (ELEIN)
of 20%,
when applied post-emergence at an application rate of 8g/ha.
Control of Setaria faberi (SETFA), a warm-climate (warm-season) grassy weed
At 14 or 15 DAA, certain test compounds (Compound A-5, A-6, A-10, A-12, A-16,
A-21, A-22
or A-23) showed percentage control of (percentage phytotoxicities on) Setaria
faberi
(SETFA) in the range of from 85% to 95%, when applied post-emergence at an
application
rate of 8g/ha.
At 14 DAA, Compound A-20 showed a percentage control of Setaria faberi (SETFA)
of 98%,
when applied post-emergence at an application rate of 8g/ha.
At 15 DAR, Compound B-1 showed a percentage control of Setaria faberi (SETFA)
of 50%,
when applied post-emergence at an application rate of 8g/ha.
At 14 DAA, Compound A-25 showed a percentage control of Setaria faberi (SETFA)
of 40%,
when applied post-emergence at an application rate of 8g/ha.
Control of Echinochloa crus-galli (ECHCG), a warm-climate (warm-season) grassy
weed
At 14 DAA, certain test compounds (Compound A-5, A-10, A-12 or A-22) showed a
percentage control of Echinochloa crus-galli (ECHCG) in the range of from 95%
to 98%,
when applied post-emergence at an application rate of 8g/ha.
At 14 DAA, Compound A-25 showed a percentage control of Echinochloa crus-galli
(ECHCG) of 45%, when applied post-emergence at an application rate of 8g/ha.

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Control of Sorghum halepense (annual) (SORHA), a warm-climate (warm-season)
grassy
weed
At 14 DAA, certain test compounds (Compound A-5, A-10, A-12, A-22 or A-25)
showed a
percentage control of Sorghum halepense (annual) (SORHA) in the range of from
70% to
99%, when applied post-emergence at an application rate of 8g/ha.
Control of Panicum dichotomiflorum (PANDI), a warm-climate (warm-season)
grassy weed
At 14 DAA, certain test compounds (Compound A-5, A-10, A-12, A-22 or A-25)
showed a
percentage control of Panicum dichotomiflorum (PAN Dl) in the range of from
85% to 99%,
when applied post-emergence at an application rate of 8g/ha.
Phytotoxicity on Glycine max (GLXMA, soybean) cultivar "Nikko"
At 14 or 15 DAA, certain test compounds (Compound A-6, A-12, A-16, A-22 or A-
25) showed
percentage phytotoxicities on Glycine max (GLXMA, soybean) cultivar "Nikko" in
the range of
from 0% to 30%, when applied post-emergence at an application rate of 120g/ha.
At 14 or 15 DAA, certain test compounds (Compound A-5, A-10, A-23 or B-1)
showed
percentage phytotoxicities on Glycine max (GLXMA, soybean) cultivar "Nikko" in
the range of
from 50% to 70%, when applied post-emergence at an application rate of
120g/ha.
At 14 or 15 DAA, certain test compounds (Compound A-20 or A-21) showed
percentage
phytotoxicities on Glycine max (GLXMA, soybean) cultivar "Nikko" of 85%, when
applied
post-emergence at an application rate of 120g/ha.
Phytotoxi city on Glycine max (GLXMA, soybean) cultivar "TMG133"
Glycine max (GLXMA, soybean) cultivar "TMG133" is Roundup Ready TM glyphosate-
tolerant
soybean cultivar TMG133, and is typically available from Monsanto in Brazil.
At 14 or 15 DAA, certain test compounds (Compound A-6, A-12, A-16, A-22 or A-
25) showed
percentage phytotoxicities on Glycine max (GLXMA, soybean) cultivar "TMG133"
in the
range of from 5% to 40%, when applied post-emergence at an application rate of
120g/ha.

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At 14 or 15 DAA, certain test compounds (Compound A-5, A-10, A-23 or B-1)
showed
percentage phytotoxicities on Glycine max (GLXMA, soybean) cultivar "TMG133"
in the
range of from 50% to 65%, when applied post-emergence at an application rate
of 120g/ha.
At 14 or 15 DAA, certain test compounds (Compound A-20 or A-21) showed
percentage
phytotoxicities on Glycine max (GLXMA, soybean) cultivar "TMG133" of 85%, when
applied
post-emergence at an application rate of 120g/ha.

Representative Drawing